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Aspen Physical

Property System

Physical Property Models


Version Number: V7.1
January 2009
Copyright (c) 1981-2009 by Aspen Technology, Inc. All rights reserved.

Aspen Physical Property System, the aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks
or registered trademarks of Aspen Technology, Inc., Burlington, MA.

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This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech
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Phone: (1) (781) 221-6400
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URL: http://www.aspentech.com
Contents
1 Introduction .........................................................................................................5
Units for Temperature-Dependent Parameters .................................................... 6
Pure Component Temperature-Dependent Properties .......................................... 7
Extrapolation Methods .................................................................................... 9

2 Thermodynamic Property Models .......................................................................11


Equation-of-State Models ...............................................................................14
ASME Steam Tables .............................................................................15
BWR-Lee-Starling................................................................................16
Benedict-Webb-Rubin-Starling ..............................................................17
Hayden-O'Connell................................................................................20
HF Equation-of-State ...........................................................................22
Ideal Gas ...........................................................................................26
Lee-Kesler..........................................................................................26
Lee-Kesler-Plöcker...............................................................................28
NBS/NRC Steam Tables........................................................................29
Nothnagel ..........................................................................................30
Copolymer PC-SAFT EOS Model .............................................................32
Peng-Robinson....................................................................................44
Standard Peng-Robinson ......................................................................46
Peng-Robinson-MHV2 ..........................................................................48
Predictive SRK (PSRK) .........................................................................48
Peng-Robinson-Wong-Sandler ...............................................................48
Redlich-Kwong ....................................................................................49
Redlich-Kwong-Aspen ..........................................................................49
Redlich-Kwong-Soave ..........................................................................50
Redlich-Kwong-Soave-Boston-Mathias....................................................52
Redlich-Kwong-Soave-Wong-Sandler .....................................................54
Redlich-Kwong-Soave-MHV2 .................................................................54
Schwartzentruber-Renon ......................................................................54
Soave-Redlich-Kwong ..........................................................................56
SRK-Kabadi-Danner.............................................................................58
SRK-ML .............................................................................................60
VPA/IK-CAPE Equation-of-State.............................................................61
Peng-Robinson Alpha Functions .............................................................66
Huron-Vidal Mixing Rules......................................................................76
MHV2 Mixing Rules ..............................................................................78
Predictive Soave-Redlich-Kwong-Gmehling Mixing Rules ...........................79
Wong-Sandler Mixing Rules ..................................................................81
Activity Coefficient Models ..............................................................................83
Bromley-Pitzer Activity Coefficient Model ................................................83
Chien-Null ..........................................................................................86

Contents 1
Constant Activity Coefficient .................................................................88
COSMO-SAC .......................................................................................88
Electrolyte NRTL Activity Coefficient Model ..............................................91
ENRTL-SAC ...................................................................................... 104
Hansen ............................................................................................ 109
Ideal Liquid ...................................................................................... 110
NRTL (Non-Random Two-Liquid).......................................................... 110
NRTL-SAC Model ............................................................................... 112
Pitzer Activity Coefficient Model ........................................................... 122
Polynomial Activity Coefficient............................................................. 133
Redlich-Kister ................................................................................... 135
Scatchard-Hildebrand ........................................................................ 135
Three-Suffix Margules ........................................................................ 136
UNIFAC Activity Coefficient Model ........................................................ 137
UNIFAC (Dortmund Modified) .............................................................. 139
UNIFAC (Lyngby Modified) .................................................................. 140
UNIQUAC Activity Coefficient Model ..................................................... 141
Van Laar Activity Coefficient Model ...................................................... 143
Wagner Interaction Parameter ............................................................ 144
Wilson Activity Coefficient Model.......................................................... 145
Wilson Model with Liquid Molar Volume................................................. 146
Vapor Pressure and Liquid Fugacity Models ..................................................... 147
Extended Antoine/Wagner/PPDS/IK-CAPE Liquid Vapor Pressure Model ..... 147
API Sour Model ................................................................................. 152
Braun K-10 Model ............................................................................. 152
Chao-Seader Pure Component Liquid Fugacity Model .............................. 153
Grayson-Streed Pure Component Liquid Fugacity Model .......................... 153
Kent-Eisenberg Liquid Fugacity Model................................................... 154
Maxwell-Bonnell Vapor Pressure Model ................................................. 155
Solid Antoine Vapor Pressure Model ..................................................... 155
DIPPR/Watson/PPDS/IK-CAPE Heat of Vaporization Model ................................. 156
DIPPR Heat of Vaporization Equation.................................................... 156
Watson Heat of Vaporization Equation .................................................. 157
PPDS Heat of Vaporization Equation ..................................................... 157
IK-CAPE Heat of Vaporization Equation................................................. 158
NIST TDE Watson Heat of Vaporization Equation .................................... 158
Clausius-Clapeyron Equation ............................................................... 159
Molar Volume and Density Models ................................................................. 159
API Liquid Volume ............................................................................. 160
Brelvi-O'Connell ................................................................................ 161
Clarke Aqueous Electrolyte Volume ...................................................... 161
COSTALD Liquid Volume..................................................................... 164
Debye-Hückel Volume ........................................................................ 165
Liquid Constant Molar Volume Model .................................................... 166
Rackett/DIPPR/PPDS/IK-CAPE Liquid Molar Volume ................................ 167
Rackett/Campbell-Thodos Mixture Liquid Volume ................................... 171
Modified Rackett Liquid Molar Volume................................................... 173
Aspen/DIPPR/IK-CAPE Solid Molar Volume ............................................ 174
Liquid Volume Quadratic Mixing Rule.................................................... 175
Heat Capacity Models ..................................................................................176
Aqueous Infinite Dilution Heat Capacity ................................................ 176
Criss-Cobble Aqueous Infinite Dilution Ionic Heat Capacity ...................... 177
DIPPR/PPDS/IK-CAPE Liquid Heat Capacity ........................................... 177

2 Contents
Aspen/DIPPR/Barin/PPDS/IK-CAPE Ideal Gas Heat Capacity .................... 181
Aspen/DIPPR/Barin/IK-CAPE Solid Heat Capacity ................................... 185
Solubility Correlations .................................................................................. 187
Henry's Constant...............................................................................187
Water Solubility ................................................................................ 188
Hydrocarbon Solubility ....................................................................... 189
Other Thermodynamic Property Models .......................................................... 190
Cavett ............................................................................................. 190
Barin Equations for Gibbs Energy, Enthalpy, Entropy, and Heat Capacity ... 190
Electrolyte NRTL Enthalpy................................................................... 193
Electrolyte NRTL Gibbs Free Energy ..................................................... 194
Liquid Enthalpy from Liquid Heat Capacity Correlation ............................ 196
Enthalpies Based on Different Reference States ..................................... 196
Helgeson Equations of State ............................................................... 201
Quadratic Mixing Rule ........................................................................ 203

3 Transport Property Models ...............................................................................204


Viscosity Models.......................................................................................... 206
Andrade Liquid Mixture Viscosity ......................................................... 206
Andrade/DIPPR/PPDS/IK-CAPE Pure Component Liquid Viscosity .............. 207
API Liquid Viscosity ........................................................................... 211
API 1997 Liquid Viscosity.................................................................... 211
Aspen Liquid Mixture Viscosity............................................................. 212
ASTM Liquid Mixture Viscosity ............................................................. 212
Chapman-Enskog-Brokaw/DIPPR/PPDS/IK-CAPE Vapor Viscosity .............. 213
Chapman-Enskog-Brokaw-Wilke Mixing Rule ......................................... 216
Chung-Lee-Starling Low-Pressure Vapor Viscosity .................................. 218
Chung-Lee-Starling Viscosity .............................................................. 220
Dean-Stiel Pressure Correction ............................................................ 222
IAPS Viscosity for Water..................................................................... 222
Jones-Dole Electrolyte Correction......................................................... 223
Letsou-Stiel ...................................................................................... 225
Lucas Vapor Viscosity ........................................................................ 225
TRAPP Viscosity Model ....................................................................... 227
Twu Liquid Viscosity .......................................................................... 227
Viscosity Quadratic Mixing Rule ........................................................... 229
Thermal Conductivity Models ........................................................................ 229
Chung-Lee-Starling Thermal Conductivity ............................................. 230
IAPS Thermal Conductivity for Water.................................................... 231
Li Mixing Rule ................................................................................... 232
Riedel Electrolyte Correction ............................................................... 232
Sato-Riedel/DIPPR/IK-CAPE Liquid Thermal Conductivity......................... 233
Solid Thermal Conductivity Polynomial ................................................. 236
Stiel-Thodos/DIPPR/PPDS/IK-CAPE Vapor Thermal Conductivity ............... 237
Stiel-Thodos Pressure Correction Model ................................................ 239
Vredeveld Mixing Rule........................................................................ 240
TRAPP Thermal Conductivity Model ...................................................... 240
Wassiljewa-Mason-Saxena Mixing Rule ................................................. 241
Diffusivity Models ........................................................................................242
Chapman-Enskog-Wilke-Lee (Binary) ................................................... 242
Chapman-Enskog-Wilke-Lee (Mixture).................................................. 243
Dawson-Khoury-Kobayashi (Binary) ..................................................... 244

Contents 3
Dawson-Khoury-Kobayashi (Mixture) ...................................................244
Nernst-Hartley .................................................................................. 245
Wilke-Chang (Binary)......................................................................... 246
Wilke-Chang (Mixture) ....................................................................... 247
Surface Tension Models................................................................................ 248
Liquid Mixture Surface Tension ............................................................ 248
API Surface Tension........................................................................... 249
IAPS Surface Tension for Water........................................................... 249
Hakim-Steinberg-Stiel/DIPPR/PPDS/IK-CAPE Liquid Surface Tension......... 249
Onsager-Samaras ............................................................................. 253
Modified MacLeod-Sugden .................................................................. 254

4 Nonconventional Solid Property Models ...........................................................255


General Enthalpy and Density Models............................................................. 255
General Density Polynomial ................................................................ 256
General Heat Capacity Polynomial........................................................ 256
Enthalpy and Density Models for Coal and Char ............................................... 257
General Coal Enthalpy Model............................................................... 260
IGT Coal Density Model ...................................................................... 266
IGT Char Density Model...................................................................... 266

5 Property Model Option Codes ...........................................................................268


Option Codes for Transport Property Models.................................................... 268
Option Codes for Activity Coefficient Models .................................................... 269
Option Codes for Equation of State Models...................................................... 271
Soave-Redlich-Kwong Option Codes............................................................... 274
Option Codes for K-Value Models................................................................... 276
Option Codes for Enthalpy Models.................................................................. 276
Option Codes for Gibbs Energy Models ........................................................... 278
Option Codes for Liquid Volume Models .......................................................... 279

Index ..................................................................................................................280

4 Contents
1 Introduction

This manual describes the property models available in the Aspen Physical
Property System and defines the parameters used in each model. The
description for each model lists the parameter names used to enter values on
the Properties Parameters forms.
This manual also lists the pure component temperature-dependent properties
that the Aspen Physical Property System can calculate from a model that
supports several equations or submodels. See Pure Component Temperature-
Dependent Properties (below).
Many parameters have default values indicated in the Default column. A dash
(–) indicates that the parameter has no default value and you must provide a
value. If a parameter is missing, calculations stop. The lower limit and upper
limit for each parameter, when available, indicate the reasonable bounds for
the parameter. The limits are used to detect grossly erroneous parameter
values.
The property models are divided into the following categories:
• Thermodynamic property models
• Transport property models
• Nonconventional solid property models
The property types for each category are discussed in separate sections. The
following table (below) provides an organizational overview of this manual.
The tables labeled Thermodynamic Property Models, Transport Property
Models, and Nonconventional Solid Property Models present detailed lists of
models. These tables also list the Aspen Physical Property System model
names, and their possible use in different phase types, for pure components
and mixtures.
Electrolyte and conventional solid property models are presented in
Thermodynamic Property Models.

1 Introduction 5
Categories of Models
Category Sections
Thermodynamic Equation-of-State Models
Property Models Activity Coefficient Models (Including Electrolyte Models)
Vapor Pressure and Liquid Fugacity Models
Heat of Vaporization Models
Molar Volume and Density Models
Heat Capacity Models
Solubility Correlations
Other
Transport Property Viscosity Models
Models Thermal Conductivity Models
Diffusivity Models
Surface Tension Models
Nonconventional Solid General Enthalpy and Density Models
Property Models Enthalpy and Density Models for Coal and Char

Units for Temperature-


Dependent Parameters
Some temperature-dependent parameters may be based on expressions
which involve logarithmic or reciprocal temperature terms. When the
coefficient of any such term is non-zero, in many cases the entire expression
must be calculated assuming that all the coefficients are in absolute
temperature units. In other cases, terms are independent from one another,
and only certain terms may require calculation using absolute temperature
units. Notes in the models containing such terms explain exactly which
coefficients are affected by this treatment.
When absolute temperature units are forced in this way, this affects the units
for coefficients you have entered as input parameters. If your input
temperature units are Fahrenheit (F), then Rankine (R) is used instead. If
your input units are Celsius (C), then Kelvin (K) is used instead.
If only constant and positive powers of temperature are present in the
expression, then your specified input units are used.
If the parameters include temperature limits, the limits are always interpreted
in user input units even if the expression is forced to absolute units.
Some equations may include a dimensionless parameter, the reduced
temperature Tr = T / Tc. This reduced temperature is calculated using
absolute temperature units. In most cases, input parameters associated with
such equations do not have temperature units.

6 1 Introduction
Pure Component Temperature-
Dependent Properties
The following table lists the pure component temperature-dependent
properties that the Aspen Physical Property System can calculate from a
model that supports several equations or submodels.
For example, the Aspen Physical Property System can calculate heat of
vaporization using these equations:
• Watson
• DIPPR
• PPDS
• IK-CAPE

Pure Component Temperature-Dependent Properties


Submodel-Selection Default DIPPR
Parameter Element Equation
Property Number Available Submodels Number
Solid Volume THRSWT/1 Aspen, DIPPR, IK-CAPE 100
Liquid Volume THRSWT/2 Aspen, DIPPR, PPDS, 105/116†
IK-CAPE
Liquid Vapor Pressure THRSWT/3 Aspen, Wagner, 101/115†
BARIN, PPDS, IK-CAPE
Heat of Vaporization THRSWT/4 Aspen, DIPPR, PPDS, 106
IK-CAPE
Solid Heat Capacity THRSWT/5 Aspen, DIPPR, BARIN, 100
IK-CAPE
Liquid Heat Capacity THRSWT/6 DIPPR, PPDS, BARIN, 100/114†
IK-CAPE
Ideal Gas Heat THRSWT/7 Aspen, DIPPR, BARIN, 107
Capacity PPDS, IK-CAPE
Second Virial THRSWT/8 DIPPR 104
Coefficient
Liquid Viscosity TRNSWT/1 Aspen, DIPPR, PPDS, 101
IK-CAPE
Vapor Viscosity TRNSWT/2 Aspen, DIPPR, PPDS, 102
IK-CAPE
Liquid Thermal TRNSWT/3 Aspen, DIPPR, PPDS, 100
Conductivity IK-CAPE
Vapor Thermal TRNSWT/4 Aspen, DIPPR, PPDS, 102
Conductivity IK-CAPE
Liquid Surface TRNSWT/5 Aspen, DIPPR, PPDS, 106
Tension IK-CAPE

Equations 114 through 116 are used as the default only for water.
Which equation is actually used to calculate the property for a given
component depends on which parameters are available. If parameters are
available for more than one equation, the Aspen Physical Property System
uses the parameters that were entered or retrieved first from the databanks.

1 Introduction 7
The selection of submodels is driven by the data hierarchy, and controlled by
the submodel-selection parameters.
The thermodynamic properties use the THRSWT (thermo switch) submodel-
selection parameter, and the transport properties use the TRNSWT (transport
switch) submodel-selection parameter.
As the previous table shows, a property is associated with an element of the
submodel-selection parameter. For example, THRSWT element 1 controls the
submodel for solid volume.
The following table shows the values for THRSWT or TRNSWT, and the
corresponding submodels.
Parameter Values
(Equation Number) Submodel
0 Aspen
1 to 116 DIPPR
200 BARIN
301 to 302 PPDS or property-specific methods
400 PML
401 to 404 IK-CAPE
501 to 515 NIST

All built-in databank components have model-selection parameters (THRSWT,


TRNSWT) that are set to use the correct equations that are consistent with
the available parameters. For example, suppose that parameters for the
DIPPR equation 106 are available for liquid surface tension. For that
component, TRNSWT element 5 is set to 106 in the databank. If you are
retrieving data from an in-house or user databank, you should store the
appropriate values for THRSWT and TRNSWT in the databank, using the
appropriate equation number. Otherwise, the Aspen Physical Property System
will search for the parameters needed for the Aspen form of the equations.
If a component is available in more than one databank, the Aspen Physical
Property System uses the data and equations based on the databank list
order on the Components Specifications Selection sheet. For example,
suppose the databank search order is ASPENPCD, then PURE10, and that the
Aspen Physical Property System cannot find the parameters for a particular
submodel (equation) in the ASPENPCD databank. If the PURE10 databank
contains parameters for another equation, the Aspen Physical Property
System will use that equation (most likely the DIPPR equation) to calculate
the property for that component.
If your calculation contains any temperature-dependent property parameters,
(such as CPIGDP for DIPPR ideal gas heat capacity, entered on the Properties
Parameters Pure Component form), the Aspen Physical Property System sets
the corresponding THRSWT and TRNSWT elements for that component to the
default values shown in the table above. This default setting might not always
be correct. If you know the equation number, you should enter it directly on
the Properties Parameters Pure-Components form. For example, suppose you
want to use the:
• DIPPR equation form of heat of vaporization (DHVLDP) for a component
• Aspen equations for the remaining temperature dependent properties

8 1 Introduction
Set the fourth element of the THRSWT parameter to 106, and the 1-3 and 5-8
elements to 0. If you want to set the other temperature-dependent properties
to use what is defined for that component in the databank, leave the element
blank.
The following table lists the available DIPPR equations and the corresponding
equation (submodel) number.

Available DIPPR Equations


Equation
Number Equation Form
100

101

102

103

104

105

106

107

114

116

For equations 114 and 116, t = 1-Tr.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
This chapter describes the Aspen, DIPPR, BARIN, IK-CAPE, and PPDS
equations for each property. For descriptions of the the BARIN equations for
heat capacity and enthalpy, see BARIN Equations for Gibbs Energy, Enthalpy,
Entropy, and Heat Capacity.

Extrapolation Methods
Many temperature dependent property models have upper and lower
temperature limits. The Aspen Physical Property System usually extrapolates
linearly beyond such limits. It calculates the slope of the property-versus-
temperature curve, or the ln(property)-versus-temperature curve for models
expressed in logarithmic form, at the upper or lower temperature limit. For
temperatures beyond the limit, it uses a linear model with this slope which
meets the curve from the equation at the temperature limit. Thus the model
is:

1 Introduction 9
For T beyond the upper or lower limit, where Tlim is that limit and Z is the
property or ln(property) as appropriate. Some liquid molar volume models are
actually molar density models which then return the reciprocal of the density
as the liquid molar volume. In these models, the extrapolation occurs for the
density calculation.
There are certain exceptions, detailed below.

Exception 1: Logarithmic Properties Based on Reciprocal


Temperature
This applies to property models expressed in the form (where a(T) includes
any additional dependency on temperature):

For these models, the extrapolation maintains the slope of ln(property) versus
1/T. This applies to the Extended Antoine vapor pressure equation and the
Andrade and DIPPR liquid viscosity equations. Note that the equation for
Henry's Constant is extrapolated by ln(Henry) versus T.

Exception 2: Aspen Ideal Gas Heat Capacity


The Aspen Ideal Gas Heat Capacity model has an explicit equation for
extrapolation at temperatures below the lower limit, which is described in the
model. At high temperatures it follows the usual rule of extrapolating
property-versus-temperature linearly.

Exception 3: No Extrapolation
The equations for certain models are used directly at all temperatures, so that
no extrapolation is performed. These models are the Wagner vapor pressure
equation, the Aly and Lee equation for the DIPPR Ideal Gas Heat Capacity
(using the CPIGDP parameter), and the Water Solubility and Hydrocarbon
Solubility models. The equations for temperature-dependent binary
interaction parameters are also used directly at all temperatures with no
extrapolation.

10 1 Introduction
2 Thermodynamic Property
Models

This section describes the available thermodynamic property models in the


Aspen Physical Property System. The following table provides a list of
available models, with corresponding Aspen Physical Property System model
names. The table provides phase types for which the model can be used and
information on use of the model for pure components and mixtures.
Aspen Physical Property System thermodynamic property models include
classical thermodynamic property models, such as activity coefficient models
and equations of state, as well as solids and electrolyte models. The models
are grouped according to the type of property they describe.

Thermodynamic Property Models


Phases: V = Vapor; L = Liquid; S = Solid. An X indicates applicable to Pure or
Mixture.

Equation-of-State Models
Property Model Model Name(s) Phase(s) Pure Mixture
ASME Steam Tables ESH2O0,ESH2O VL X —
BWR-Lee-Starling ESBWR0, ESCSTBWR V L X X
Benedict-Webb-Rubin-Starling ESBWRS, ESBWRS0 VL X X
Hayden-O'Connell ESHOC0,ESHOC V X X
HF equation-of-state ESHF0, ESHF V X X
Ideal Gas ESIG0, ESIG V X X
Lee-Kesler ESLK VL — X
Lee-Kesler-Plöcker ESLKP0,ESLKP VL X X
NBS/NRC Steam Tables ESSTEAM0,ESSTEAM VL X —
Nothnagel ESNTH0,ESNTH V X X
PC-SAFT ESPSAFT, ESPSAFT0 VL X X
Peng-Robinson ESPR0, ESPR VL X X
Standard Peng-Robinson ESPRSTD0,ESPRSTD VL X X
Peng-Robinson-Wong-Sandler ESPRWS0,ESPRWS VL X X
Peng-Robinson-MHV2 ESPRV20,ESPRV2 VL X X

2 Thermodynamic Property Models 11


Property Model Model Name(s) Phase(s) Pure Mixture
Predictive SRK ESRKSV10, ESRKSV1 V L X X
Redlich-Kwong ESRK0, ESRK V X X
Redlich-Kwong-Aspen ESRKA0,ESRKA VL X X
Redlich-Kwong-Soave ESRKSTD0,ESRKSTD VL X X
Redlich-Kwong-Soave-Boston- ESRKS0, ESRKS VL X X
Mathias
Redlich-Kwong-Soave-Wong- ESRKSWS0, ESRKSWS V L X X
Sandler
Redlich-Kwong-Soave-MHV2 ESRKSV20, ESRKSV2 V L X X
Schwartzentruber-Renon ESRKU0,ESRKU VL X X
Soave-Redlich-Kwong ESSRK0, ESSRK VL X X
SRK-Kabadi-Danner ESSRK0, ESSRK VL X X
SRK-ML ESRKSML0, ESRKSML V L X X
VPA/IK-CAPE equation-of-state ESVPA0, ESVPA V X X
Peng-Robinson Alpha functions — VL X —
RK-Soave Alpha functions — VL X —
Huron-Vidal mixing rules — VL — X
MHV2 mixing rules — VL — X
PSRK mixing rules — VL — X
Wong-Sandler mixing rules — VL — X

Activity Coefficient Models (Including Electrolyte Models)


Property Model Model Name Phase(s) Pure Mixture
Bromley-Pitzer GMPT2 L — X
Chien-Null GMCHNULL L — X
Constant Activity Coefficient GMCONS S — X
COSMO-SAC COSMOSAC L — X
Electrolyte NRTL GMELC L L1 L2 — X
ENRTL-SAC ENRTLSAC L — X
Hansen HANSEN L — X
Ideal Liquid GMIDL L — X
NRTL(Non-Random-Two-Liquid) GMRENON L L1 L2 — X
NRTL-SAC NRTLSAC L — X
Pitzer GMPT1 L — X
Polynomial Activity Coefficient GMPOLY LS — X
Redlich-Kister GMREDKIS LS — X
Scatchard-Hildebrand GMXSH L — X
Three-Suffix Margules GMMARGUL LS — X
UNIFAC GMUFAC L L1 L2 — X
UNIFAC (Lyngby modified) GMUFLBY L L1 L2 — X
UNIFAC (Dortmund modified) GMUFDMD L L1 L2 — X
UNIQUAC GMUQUAC L L1 L2 — X
van Laar GMVLAAR L — X

12 2 Thermodynamic Property Models


Property Model Model Name Phase(s) Pure Mixture
Wagner interaction parameter GMWIP S — X
Wilson GMWILSON L — X
Wilson model with liquid molar GMWSNVOL L — X
volume

Vapor Pressure and Liquid Fugacity Models


Property Model Model Name Phase(s) Pure Mixture
Extended Antoine/Wagner PL0XANT L L1 L2 X —
API Sour SWEQ L — X
Braun K-10 BK10 L — X
Chao-Seader PHL0CS L X —
Grayson-Streed PHL0GS L X —
Kent-Eisenberg ESAMINE L — X
Maxwell-Bonnell PL0MXBN L L1 L2 X —
Solid Antoine PS0ANT S X —

Heat of Vaporization Models


Property Model Model Name Phase(s) Pure Mixture
DIPPR/Watson/PPDS/IK-CAPE DHVLWTSN L X —
Clausius-Clapeyron Equation DHVLWTSN L X —

Molar Volume and Density Models


Property Model Model Name Phase(s) Pure Mixture
API Liquid Volume VL2API L — X
Brelvi-O'Connell VL1BROC L — X
Clarke Aqueous Electrolyte VAQCLK L — X
Volume
COSTALD Liquid Volume VL0CTD,VL2CTD L X X
Debye-Hückel Volume VAQDH L — X
Liquid Constant Molar Volume VL0CONS L X —
Rackett / DIPPR/ PPDS / IK- VL0RKT,VL2RKT L X —
CAPE Liquid Volume
Rackett/Campbell-Thodos VL2RKT L X X
Mixture Liquid Volume
Modified Rackett VL2MRK L X X
Aspen/DIPPR/IK-CAPE Solid VS0POLY S X —
Molar Volume
Liquid Volume Quadratic Mixing VL2QUAD L — X
Rule

Heat Capacity Models


Property Model Model Name Phase(s) Pure Mixture
Aqueous Infinite Dilution Heat — L — X
Capacity Polynomial

2 Thermodynamic Property Models 13


Property Model Model Name Phase(s) Pure Mixture
Criss-Cobble Aqueous Infinite — L — X
Dilution Ionic Heat Capacity
DIPPR / PPDS / IK-CAPE Liquid HL0DIP L X —
Heat Capacity
Aspen / DIPPR / Barin / PPDS / — V X X
IK-CAPE Ideal Gas Heat
Capacity
Aspen / DIPPR / Barin / IK-CAPE HS0POLY S X —
Solids Heat Capacity

Solubility Correlation Models


Property Model Model Name Phase(s) Pure Mixture
Henry's constant HENRY1 L — X
Water solubility — L — X
Hydrocarbon solubility — L — X

Other Models
Property Model Model Name Phase(s) Pure Mixture
Cavett Liquid Enthalpy DHL0CVT, DHL2CVT L X X
Departure
BARIN Equations for Gibbs — SLV X —
Energy, Enthalpy, Entropy and
Heat Capacity
Electrolyte NRTL Enthalpy HAQELC, HMXELC L — X
Electrolyte NRTL Gibbs Energy GAQELC, GMXELC L — X
Liquid Enthalpy from Liquid Heat DHL0DIP L X X
Capacity Correlation
Enthalpies Based on Different DHL0HREF LV X X
Reference States
Helgeson Equations of State — L — X
Quadratic Mixing Rule — LV — X

Equation-of-State Models
The Aspen Physical Property System has the following built-in equation-of-
state property models. This section describes the equation-of-state property
models available.
Model Type
ASME Steam Tables Fundamental
BWR-Lee-Starling Virial
Benedict-Webb-Rubin-Starling Virial
Hayden-O'Connell Virial and association
HF Equation-of-State Ideal and association
Huron-Vidal mixing rules Mixing rules
Ideal Gas Ideal

14 2 Thermodynamic Property Models


Model Type
Lee-Kesler Virial
Lee-Kesler-Plöcker Virial
MHV2 mixing rules Mixing rules
NBS/NRC Steam Tables Fundamental
Nothnagel Ideal
PC-SAFT Association
Peng-Robinson Cubic
Standard Peng-Robinson Cubic
Peng-Robinson Alpha functions Alpha functions
Peng-Robinson-MHV2 Cubic
Peng-Robinson-Wong-Sandler Cubic
Predictive SRK Cubic
PSRK mixing rules Mixing rules
Redlich-Kwong Cubic
Redlich-Kwong-Aspen Cubic
Standard Redlich-Kwong-Soave Cubic
Redlich-Kwong-Soave-Boston-Mathias Cubic
Redlich-Kwong-Soave-MHV2 Cubic
Redlich-Kwong-Soave-Wong-Sandler Cubic
RK-Soave Alpha functions Alpha functions
Schwartzentruber-Renon Cubic
Soave-Redlich-Kwong Cubic
SRK-Kabadi-Danner Cubic
SRK-ML Cubic
VPA/IK-CAPE equation-of-state Ideal and association
Wong-Sandler mixing rules Mixing rules

ASME Steam Tables


The ASME steam tables are implemented like any other equation-of-state in
the Aspen Physical Property System. The steam tables can calculate any
thermodynamic property of water or steam and form the basis of the STEAM-
TA property method. There are no parameter requirements. The ASME steam
tables are less accurate than the NBS/NRC steam tables.

References
ASME Steam Tables, Thermodynamic and Transport Properties of Steam,
(1967).
K. V. Moore, Aerojet Nuclear Company, prepared for the U.S. Atomic Energy
Commision, ASTEM - A Collection of FORTRAN Subroutines to Evaluate the
1967 ASME equations of state for water/steam and derivatives of these
equations.

2 Thermodynamic Property Models 15


BWR-Lee-Starling
The Benedict-Webb-Rubin-Lee-Starling equation-of-state is the basis of the
BWR-LS property method. It is a generalization by Lee and Starling of the
virial equation-of-state for pure fluids by Benedict, Webb and Rubin. The
equation is used for non-polar components, and can manage hydrogen-
containing systems.
General Form:

Where:

Mixing Rules:

Where:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TCBWR Tci TC X 5.0 2000.0 TEMPERATURE
VCBWR Vci* VC X 0.001 3.5 MOLE-
VOLUME
BWRGMA γi OMEGA X -0.5 3.0 —

BWRKV εij 0 X -5.0 1.0 —

BWRKT ηij 0 X -5.0 1.0 —

Binary interaction parameters BWRKV and BWRKT are available in the Aspen
Physical Property System for a large number of components. (See Physical
Property Data, Chapter 1).

References
M.R. Brulé, C.T. Lin, L.L. Lee, and K.E. Starling, AIChE J., Vol. 28, (1982) p.
616.
Brulé et al., Chem. Eng., (Nov., 1979) p. 155.

16 2 Thermodynamic Property Models


Watanasiri et al., AIChE J., Vol. 28, (1982) p. 626.

Benedict-Webb-Rubin-Starling
The Benedict-Webb-Rubin-Starling equation-of-state is the basis of the BWRS
property method. It is a modification by Han and Starling of the virial
equation-of-state for pure fluids by Benedict, Webb and Rubin. This equation-
of-state can be used for hydrocarbon systems that include the common light
gases, such as H2S, CO2 and N2.
The form of the equation-of-state is:

Where:

2 Thermodynamic Property Models 17


kij = kji

In the mixing rules given above, A0i, B0i, C0i, D0i, E0i, ai, bi, ci, di, αi, γi are pure
component constants which can be input by the user. If the values of these
parameters are not given, the Aspen Physical Property System will calculate
them using the critical temperature, the critical volume (or critical density),
the acentric factor and generalized correlations given by Han and Starling.
When water is present, by default Benedict-Webb-Rubin-Starling uses the
steam table to calculate the enthalpy, entropy, Gibbs energy, and molar
volume of water. The total properties are mole-fraction averages of these
values with the properties calculated by the equation of state for other
components. Fugacity coefficient is not affected. An option code can disable
this use of the steam table.
For best results, the binary parameter kij must be regressed using phase-
equilibrium data such as VLE data.
Parameter SymbolDefault MDS Lower Upper Units
Name/ Limit Limit
Element
BWRSTC Tci TC x 5.0 2000.0 TEMPERATURE
BWRSVC Vci VC x 0.001 3.5 MOLE-VOLUME
BWRSOM ωi OMEGA x –0.5 2.0 –
BWRSA/1 B0i fcn(ωi ,Vci , Tci) x – – MOLE-VOLUME
BWRSA/2 A0i fcn(ωi ,Vci , Tci) x – – PRESSURE * MOLE-
VOL^2
BWRSA/3 C0i fcn(ωi ,Vci , Tci) x – – PRESSURE *
TEMPERATURE^2 *
MOLE-VOLUME^2
BWRSA/4 γi fcn(ωi ,Vci , Tci) x – – MOLE-VOLUME^2

BWRSA/5 bi fcn(ωi ,Vci , Tci) x – – MOLE-VOLUME^2


BWRSA/6 ai fcn(ωi ,Vci , Tci) x – – PRESSURE * MOLE-
VOL^3
BWRSA/7 αi fcn(ωi ,Vci , Tci) x – – MOLE-VOLUME^3
BWRSA/8 ci fcn(ωi ,Vci , Tci) x – – PRESSURE *
TEMPERATURE^2 *
MOLE-VOLUME^3
BWRSA/9 D0i fcn(ωi ,Vci , Tci) x – – PRESSURE *
TEMPERATURE^3 *
MOLE-VOLUME^2
BWRSA/10 di fcn(ωi ,Vci , Tci) x – – PRESSURE *
TEMPERATURE * MOLE-
VOLUME^3

18 2 Thermodynamic Property Models


Parameter SymbolDefault MDS Lower Upper Units
Name/ Limit Limit
Element
BWRSA/11 E0i fcn(ωi ,Vci , Tci) x – – PRESSURE *
TEMPERATURE^4 *
MOLE-VOLUME^2
BWRAIJ kij – x – – –

Constants Used with the correlations of Han and Starling


Parameter Methane Ethane Propane n-Butane
B0i 0.723251 0.826059 0.964762 1.56588
A0i 7520.29 13439.30 18634.70 32544.70
8 9 9
C0i 2.71092x10 2.95195x10 7.96178x10 1.37436x1010
10 11 11
D0i 1.07737x10 2.57477x10 4.53708x10 3.33159x1011
E0i 3.01122x1010 1.46819x1013 2.56053x1013 2.30902x1012
bi 0.925404 3.112060 5.462480 9.140660
ai 2574.89 22404.50 40066.40 71181.80
7
di 47489.1 702189.0 1.50520x10 3.64238x107
αi 0.468828 0.909681 2.014020 4.009850
ci 4.37222x108 6.81826x109 2.74461x1010 7.00044x1010
γi 1.48640 2.99656 4.56182 7.54122

Parameter n-Pentane n-Hexane n-Heptane n-Octane


B0i 2.44417 2.66233 3.60493 4.86965
A0i 51108.20 45333.10 77826.90 81690.60
10 10 10
C0i 2.23931x10 5.26067x10 6.15662x10 9.96546x1010
12 12 12
D0i 1.01769x10 5.52158x10 7.77123x10 7.90575x1012
E0i 3.90860x1013 6.26433x1014 6.36251x1012 3.46419x1013
bi 16.607000 29.498300 27.441500 10.590700
ai 162185.00 434517.00 359087.00 131646.00
7 7
di 3.88521x10 3.27460x10 8351150.0 1.85906x108
αi 7.067020 9.702300 21.878200 34.512400
ci 1.35286x1011 3.18412x1011 3.74876x1011 6.42053x1011
γi 11.85930 14.87200 24.76040 21.98880

References
M. Benedict, G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, (1940), p.
334.
M. S. Han, and K. E. Starling , "Thermo Data Refined for LPG. Part 14:
Mixtures", Hydrocarbon Processing, Vol. 51, No. 5, (1972), p.129.
K. E. Starling, "Fluid Themodynamic Properties for Light Petroleum Systems",
Gulf Publishing Co., Houston, Texas (1973).

2 Thermodynamic Property Models 19


Hayden-O'Connell
The Hayden-O'Connell equation-of-state calculates thermodynamic properties
for the vapor phase. It is used in property methods NRTL-HOC, UNIF-HOC,
UNIQ-HOC, VANL-HOC, and WILS-HOC, and is recommended for nonpolar,
polar, and associating compounds. Hayden-O'Connell incorporates the
chemical theory of dimerization. This model accounts for strong association
and solvation effects, including those found in systems containing organic
acids, such as acetic acid. The equation-of-state is:

Where:

• For nonpolar, non-associating species:

, with

, where

• For polar, associating species:

, with

, where

• For chemically bonding species:

, and

Cross-Interactions
The previous equations are valid for dimerization and cross-dimerization if
these mixing rules are applied:

20 2 Thermodynamic Property Models


η = 0 unless a special solvation contribution can be justified (for example, i
and j are in the same class of compounds). Many η values are present in the
Aspen Physical Property System.

Chemical Theory

When a compound with strong association is present in a mixture,


the entire mixture is treated according to the chemical theory of dimerization.
The chemical reaction for the general case of a mixture of dimerizing
components i and j is:

Where i and j refer to the same component.


The equation-of-state becomes:

with
In this case, molar volume is equal to V/nt.
This represents true total volume over the true number of species nt.
However, the reported molar volume is V/na.
This represents the true total volume over the apparent number of species na.
If dimerization does not occur, na is defined as the number of species. V/na
reflects the apparently lower molar volume of an associating gas mixture.
The chemical equilibrium constant for the dimerization reaction on pressure
basis Kp, is related to the true mole fractions and fugacity coefficients:

Where:
yi and yj = True mole fractions of monomers
yij = True mole fraction of dimer

2 Thermodynamic Property Models 21


ϕi = True fugacity coefficient of component i
Kij = Equilibrium constant for the dimerization of i and j, on a
pressure basis
=

δij = 1 for i=j


= 0 for

Apparent mole fractions yia are reported, but in the calculation real mole
fractions yi, yj, and yij are used.
The heat of reaction due to each dimerization is calculated according to:

The sum of the contributions of all dimerization reactions, corrected for the
ratio of apparent and true number of moles is added to the molar enthalpy
departure .
Parameter Name/ Symbol Default MDS Lower Upper Units
Element Limit Limit
TC Tci — — 5.0 2000.0 TEMPERATURE
PC pci — — 105 108 PRESSURE
RGYR rigyr — — 10 -11
5x10 -9
LENGTH
-24
MUP pi — — 0.0 5x10 DIPOLEMOMENT
HOCETA η 0.0 X — — —

The binary parameters HOCETA for many component pairs are available in the
Aspen Physical Property System. These parameters are retrieved
automatically when you specify any of the following property methods: NRTL-
HOC, UNIF-HOC, UNIQ-HOC, VANL-HOC, and WILS-HOC.

References
J.G. Hayden and J.P. O'Connell, "A Generalized Method for Predicting Second
Virial Coefficients," Ind. Eng. Chem., Process Des. Dev., Vol. 14,No. 3,
(1974), pp. 209 – 216.

HF Equation-of-State
HF forms oligomers in the vapor phase. The non-ideality in the vapor phase is
found in important deviations from ideality in all thermodynamic properties.
The HF equation accounts for the vapor phase nonidealities. The model is
based on chemical theory and assumes the formation of hexamers.
Species like HF that associate linearly behave as single species. For example,
they have a vapor pressure curve, like pure components. The component on
which a hypothetical unreacted system is based is often called the apparent
(or parent) component. Apparent components react to the true species.
Electrolyte Calculation in Physical Property Methods discusses apparent and

22 2 Thermodynamic Property Models


true species. Abbott and van Ness (1992) provide details and basic
thermodynamics of reactive systems.
The temperature-dependent hexamerization equilibrium constant, can fit the
experimentally determined association factors. The built-in functionality is:
(1)

The constants C0 and C1 are from Long et al. (1943), and C2 and C3 are set to
0. The correlation is valid between 270 and 330 K, and can be extrapolated to
about 370 K (cf. sec. 4). Different sets of constants can be determined by
experimental data regression.

Molar Volume Calculation


The non-ideality of HF is often expressed using the association factor, f,
indicating the ratio of apparent number of species to the real number or
species. Assuming the ideal gas law for all true species in terms of (p, V, T)
behavior implies:
(2)

Where the true number of species is given by 1/f. The association factor is
easily determined from (p, V, T) experiments. For a critical evaluation of data
refer to Vanderzee and Rodenburg (1970).
If only one reaction is assumed for a mixture of HF and its associated species,
(refer to Long et al., 1943), then:
(3)

If p1 represents the true partial pressure of the HF monomer, and p6


represents the true partial pressure of the hexamer, then the equilibrium
constant is defined as:
(4)

The true total pressure is:


p = p1 + p6 (5)
If all hexamer were dissociated, the apparent total pressure would be the
hypothetical pressure where:
pa = p1 + 6p6 = p + 5p6 (6)
When physical ideality is assumed, partial pressures and mole fractions are
proportional. The total pressure in equation 5 represents the true number of
species. The apparent total pressure from equation 6 represents the apparent
number of species:
(7)

2 Thermodynamic Property Models 23


Note that the outcome of equation 7 is independent of the assumption of
ideality. Equation 7 can be used to compute the number of true species 1/f
for a mixture containing HF, but the association factor is defined differently.
If p1 and p6 are known, the molar volume or density of a vapor containing HF
can be calculated using equations 2 and 7. The molar volume calculated is the
true molar volume for 1 apparent mole of HF. This is because the volume of 1
mole of ideal gas (the true molar volume per true number of moles) is always
equal to about 0.0224 m3/mol at 298.15 K.

True Mole Fraction (Partial Pressure) Calculation


If you assume the ideal gas law for a mixture containing HF, the apparent HF
mole fraction is:
(8)

The denominator of equation 8 is given by equation 6. The numerator (the


apparent partial pressure of HF) is the hypothetical partial pressure only if all
of the hexamer was dissociated. If you substitute equation 4, then equation 8
becomes:
(9)

K is known from Long et al., or can be regressed from (p,V,T) data. The
apparent mole fraction of HF, ya, is known to the user and the simulator, but
p1, or y = p1/p must also be known in order to calculate the thermodynamic
properties of the mixture. Equation 9 must be solved for p1.
Equation 9 can be written as a polynomial in p1 of degree 6:
K(6 - 5ya)(p1)6 + p1 - pya = 0 (9a)
A second order Newton-Raphson technique is used to determine p1. Then p6
can be calculated by equation 5, and f is known (equation 7).

Gibbs Energy and Fugacity


The apparent fugacity coefficient is related to the true fugacity coefficient and
mole fractions:
(10)

Equation 10 represents a correction to the ideal mixing term of the fugacity.


The ratio of the true number of species to the apparent number of species is
similar to the correction applied in equation 2. Since the ideal gas law is
assumed, the apparent fugacity coefficient is given by the equation. All
variables on the right side are known.
(11)

24 2 Thermodynamic Property Models


For pure HF, ya = 1:

From the fugacity coefficient, the Gibbs energy departure of the mixture or
pure apparent components can be calculated:
(12)

(12a)

Enthalpy and Entropy


For the enthalpy departure, the heat of reaction is considered. For an
arbitrary gas phase reaction:
(13)

(14)

Where μi* is the pure component thermodynamic potential or molar Gibbs


energy of a component. Equation 4 represents the first two terms of the
general equation 14. The second or third equality relates the equilibrium
constant to the Gibbs energy of reaction, which is thus related to the enthalpy
of reaction:
(15)

All components are assumed to be ideal. The enthalpy departure is equal to


the heat of reaction, per apparent number of moles:
(16)

(17)

From the Gibbs energy departure and enthalpy departure, the entropy
departure can be calculated:
(18)

Temperature derivatives for the thermodynamic properties can be obtained


by straightforward differentiation.

Usage
The HF equation-of-state should only be used for vapor phase calculations. It
is not suited for liquid phase calculations.

2 Thermodynamic Property Models 25


The HF equation-of-state can be used with any activity coefficient model for
nonelectrolyte VLE. Using the Electrolyte NRTL model and the data package
MHF2 is strongly recommended for aqueous mixtures (de Leeuw and
Watanasiri, 1993).
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
ESHFK/1 C0 43.65 — — — —
ESHFK/2 C1 -8910 — — — —
ESHFK/3 C2 0 — — — —
ESHFK/4 C3 0 — — — —

References
M. M. Abbott and H. C. van Ness, "Thermodynamics of Solutions Containing
Reactive Species, a Guide to Fundamentals and Applications," Fluid Phase Eq.,
Vol. 77, (1992) pp. 53 – 119.
V. V. De Leeuw and S. Watanasiri, "Modelling Phase Equilibria and Enthalpies
of the System Water and Hydroflouric Acid Using an HF Equation-of-state in
Conjunction with the Electrolyte NRTL Activity Coefficient Model," Paper
presented at the 13th European Seminar on Applied Thermodynamics, June 9
– 12, Carry-le-Rouet, France, 1993.
R. W. Long, J. H. Hildebrand, and W. E. Morrell, "The Polymerization of
Gaseous Hydrogen and Deuterium Flourides," J. Am. Chem. Soc., Vol. 65,
(1943), pp. 182 – 187.
C. E. Vanderzee and W. WM. Rodenburg, "Gas Imperfections and
Thermodynamic Excess Properties of Gaseous Hydrogen Fluoride," J. Chem.
Thermodynamics, Vol. 2, (1970), pp. 461 – 478.

Ideal Gas
The ideal gas law (ideal gas equation-of-state) combines the laws of Boyle
and Gay-Lussac. It models a vapor as if it consisted of point masses without
any interactions. The ideal gas law is used as a reference state for equation-
of-state calculations, and can be used to model gas mixtures at low pressures
(without specific gas phase interactions).
The equation is:
p = RT / Vm

Lee-Kesler
This equation-of-state model is based on the work of Lee and Kesler (1975).
In this equation, the volumetric and thermodynamic properties of fluids based
on the Curl and Pitzer approach (1958) have been analytically represented by
a modified Benedict-Webb-Rubin equation-of-state (1940). The model
calculates the molar volume, enthalpy departure, Gibbs free energy
departure, and entropy departure of a mixture at a given temperature,
pressure, and composition for either a vapor or a liquid phase. Partial

26 2 Thermodynamic Property Models


derivatives of these quantities with respect to temperature can also be
calculated.
Unlike the other equation-of-state models, this model does not calculate
fugacity coefficients.
The compressibility factor and other derived thermodynamic functions of
nonpolar and slightly polar fluids can be adequately represented, at constant
reduced temperature and pressure, by a linear function of the acentric factor.
In particular, the compressibility factor of a fluid whose acentric factor is ω, is
given by the following equation:
Z = Z(0) + ωZ(1)
Where:
Z(0) = Compressibility factor of a simple fluid (ω = 0)
Z(1) = Deviation of the compressibility factor of the real fluid from Z(0)
Z(0) and Z(1) are assumed universal functions of the reduced temperature and
pressure.
Curl and Pitzer (1958) were quite successful in correlating thermodynamic
and volumetric properties using the above approach. Their application
employed tables of properties in terms of reduced temperature and pressure.
A significant weakness of this method is that the various properties (for
example, entropy departure and enthalpy departure) will not be exactly
thermodynamically consistent with each other. Lee and Kesler (1975)
overcame this drawback by an analytic representation of the tables with an
equation-of-state. In addition, the range was extended by including new data.
In the Lee-Kesler implementation, the compressibility factor of any fluid has
been written in terms of a simple fluid and a reference as follows:

In the above equation both Z(0) and Z(1) are represented as generalized
equations of the BWR form in terms of reduced temperature and pressure.
Thus,

Equations for the enthalpy departure, Gibbs free energy departure, and
entropy departure are obtained from the compressibility factor using standard
thermodynamic relationships, thus ensuring thermodynamic consistency.
In the case of mixtures, mixing rules (without any binary parameters) are
used to obtain the mixture values of the critical temperature and pressure,
and the acentric factor.
This equation has been found to provide a good description of the volumetric
and thermodynamic properties of mixtures containing nonpolar and slightly
polar components.
Symbol Parameter Name Default Definition
Tc TCLK TC Critical temperature
Pc PCLK PC Critical pressure

2 Thermodynamic Property Models 27


Symbol Parameter Name Default Definition
ω OMGLK OMEGA Acentric factor

References
M. Benedict, G. B. Webb, and L. C. Rubin, J. Chem. Phys., Vol. 8, (1940), p.
334.
R. F. Curl and K.S. Pitzer, Ind. Eng. Chem., Vol. 50, (1958), p. 265.
B. I. Lee and M.G. Kesler, AIChE J., Vol. 21, (1975), p. 510.

Lee-Kesler-Plöcker
The Lee-Kesler-Plöcker equation-of-state is the basis for the LK-PLOCK
property method. This equation-of-state applies to hydrocarbon systems that
include the common light gases, such as H2S and CO2. It can be used in gas-
processing, refinery, and petrochemical applications.
The general form of the equation is:

Where:

The fo and fR parameters are functions of the BWR form. The fo parameter is
for a simple fluid, and fR is for reference fluid n-octane.

The mixing rules are:


Vcm =

ω =

Zm =

Where:
Vcij =

Tcij =

28 2 Thermodynamic Property Models


Zci =

kij = kji
The binary parameter kij is determined from phase-equilibrium data
regression, such as VLE data. The Aspen Physical Property System stores the
binary parameters for a large number of component pairs. These binary
parameters are used automatically with the LK-PLOCK property method. If
binary parameters for certain component pairs are not available, they can be
estimated using built-in correlations. The correlations are designed for binary
interactions among the components CO, CO2, N2, H2, CH4 alcohols and
hydrocarbons. If a component is not CO, CO2, N2, H2, CH4 or an alcohol, it is
assumed to be a hydrocarbon.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
TCLKP Tci TC x 5.0 2000.0 TEMPERATURE
PCLKP pci PC x PRESSURE

VCLKP Vci VC x 0.001 3.5 MOLE-


VOLUME
OMGLKP ωI OMEGA x -0.5 2.0 —
LKPZC Zci fcn(ω) (Method 1) x 0.1 0.5 —
fcn(pci,Vci,Tci)
(Method 2)
LKPKIJ kij fcn(TciVci / TcjVcj) x 5.0 5.0 —

Method 1 is the default for LKPZC; Method 2 can be invoked by setting the
value of LKPZC equal to zero.
Binary interaction parameters LKPKIJ are available for a large number of
components in the Aspen Physical Property System.

References
B.I. Lee and M.G. Kesler, AIChE J., Vol. 21, (1975) p. 510; errata: AIChE J.,
Vol. 21, (1975) p. 1040.
V. Plöcker, H. Knapp, and J.M. Prausnitz, Ind. Eng. Chem., Process Des. Dev.,
Vol. 17, (1978), p. 324.

NBS/NRC Steam Tables


The NBS/NRC Steam Tables are implemented like any other equation-of-state
in the Aspen Physical Property System. These steam tables can calculate any
thermodynamic property of water. The tables form the basis of the
STEAMNBS and STMNBS2 property methods. There are no parameter
requirements. They are the most accurate steam tables in the Aspen Physical
Property System. The STMNBS2 model uses the same equations as
STEAMNBS but with different root search method. The STEAMNBS method is

2 Thermodynamic Property Models 29


recommended for use with the SRK, BWRS, MXBONNEL and GRAYSON2
property methods.

References
L. Haar, J.S. Gallagher, and J.H. Kell, "NBS/NRC Steam Tables," (Washington:
Hemisphere Publishing Corporation, 1984).

Nothnagel
The Nothnagel equation-of-state calculates thermodynamic properties for the
vapor phase. It is used in property methods NRTL-NTH, UNIQ-NTH, VANL-
NTH, and WILS-NTH. It is recommended for systems that exhibit strong vapor
phase association. The model incorporates the chemical theory of
dimerization to account for strong association and solvation effects, such as
those found in organic acids, like acetic acid. The equation-of-state is:

Where:
b =

bij =

nc = Number of components in the mixture


The chemical reaction for the general case of a mixture of dimerizing
components i and j is:

The chemical equilibrium constant for the dimerization reaction on pressure


basis Kp is related to the true mole fractions and fugacity coefficients:

Where:
yi and yj = True mole fractions of monomers
yij = True mole fraction of dimer
ϕi = True fugacity coefficient of component i
Kij = Equilibrium constant for the dimerization of i and j, on a
pressure basis

30 2 Thermodynamic Property Models


When accounting for chemical reactions, the number of true species nt in the
mixture changes. The true molar volume V/nt is calculated from the
equation-of-state. Since both V and nt change in about the same proportion,
this number does not change much. However, the reported molar volume is
the total volume over the apparent number of species: V/na. Since the
apparent number of species is constant and the total volume decreases with
association, the quantity V/na reflects the apparent contraction in an
associating mixture.
The heat of reaction due to each dimerization can be calculated:

The heat of reaction for the mixed dimerization of components i and j is by


default the arithmetic mean of the heats of reaction for the dimerizations of

the individual components. Parameter is a small empirical correction


factor to this value:

The sum of the contributions of all dimerization reactions, corrected for the
ratio of apparent and true number of moles, is added to the molar enthalpy
departure:

The equilibrium constants can be computed using either built-in calculations


or parameters you entered.
• Built-in correlations:

The pure component parameters b, d, and p are stored in the Aspen


Physical Property System for many components.
Parameters you entered:

In this method, you enter Ai, Bi, Ci, and Di on the Properties Parameters
Unary.T-Dependent form. The units for Kii is pressure-1; use absolute units for
temperature. If you enter Kii and Kjj, then Kij is computed from

If you enter Ai, Bi, Ci, and Di, the equilibrium constants are computed using
the parameters you entered. Otherwise the equilibrium constants are
computed using built-in correlations.
Parameter Symbol Default Lower Upper Limit Units
Name/Element Limit
TC Tci — 5.0 2000.0 TEMPERATURE
TB Tbi — 4.0 2000.0 TEMPERATURE
5 8
PC pci — 10 10 PRESSURE
NTHA/1 bi 0.199 RTci / pci 0.01 1.0 MOLE-VOLUME
NTHA/2 di 0.33 0.01 3.0 —

2 Thermodynamic Property Models 31


Parameter Symbol Default Lower Upper Limit Units
Name/Element Limit
NTHA/3 pi 0 0.0 1.0 —
NTHK/1 Ai — — — PRESSURE
NTHK/2 Bi 0 — — TEMPERATURE
NTHK/3 Ci 0 — — TEMPERATURE
NTHK/4 Di 0 — — TEMPERATURE

NTHDDH 0 — — MOLE-
ENTHALPY

† For the following systems, the values given in Nothnagel et al., 1973 are
used by default:
• Methyl chloride/acetone
• Acetonitrile/acetaldehyde
• Acetone/chloroform
• Chloroform/diethyl amine
• Acetone/benzene
• Benzene/chloroform
• Chloroform/diethyl ether
• Chloroform/propyl formate
• Chloroform/ethyl acetate
• Chloroform/methyl acetate
• Chloroform/methyl formate
• Acetone/dichloro methane
• n-Butane/n-perfluorobutane
• n-Pentane/n-perfluoropentane
• n-Pentane/n-perfluorohexane

References
K.-H. Nothnagel, D. S. Abrams, and J.M. Prausnitz, "Generalized Correlation
for Fugacity Coefficients in Mixtures at Moderate Pressures," Ind. Eng. Chem.,
Process Des. Dev., Vol. 12, No. 1 (1973), pp. 25 – 35.

Copolymer PC-SAFT EOS Model


This section describes the Copolymer Perturbed-Chain Statistical Associating
Fluid Theory (PC-SAFT). This equation-of-state model is used through the PC-
SAFT property method.
The copolymer PC-SAFT represents the completed PC-SAFT EOS model
developed by Sadowski and co-workers (Gross and Sadowski, 2001, 2002a,
2002b; Gross et al., 2003; Becker et al., 2004; Kleiner et al., 2006). Unlike
the PC-SAFT EOS model (POLYPCSF) in Aspen Plus, the copolymer PC-SAFT
includes the association and polar terms and does not apply mixing rules to
calculate the copolymer parameters from its segments. Its applicability covers
fluid systems from small to large molecules, including normal fluids, water,
alcohols, and ketones, polymers and copolymers and their mixtures.

32 2 Thermodynamic Property Models


Copolymer PC-SAFT Fundamental Equations
The copolymer PC-SAFT model is based on the perturbation theory. The
underlying idea is to divide the total intermolecular forces into repulsive and
attractive contributions. The model uses a hard-chain reference system to
account for the repulsive interactions. The attractive forces are further divided
into different contributions, including dispersion, polar, and association.
Using a generated function, ψ, the copolymer PC-SAFT model in general can
be written as follows:

where ψhc, ψdisp, ψassoc, and ψpolar are contributions due to hard-chain fluids,
dispersion, association, and polarity, respectively.

The generated function ψ is defined as follows:

where ares is the molar residual Helmholtz energy of mixtures, R is the gas
constant, T is the temperature, ρ is the molar density, and Zm is the
compressibility factor; ares is defined as:

where a is the Helmholtz energy of a mixture and aig is the Helmholtz energy
of a mixture of ideal gases at the same temperature, density and composition
xi. Once ψ is known, any other thermodynamic function of interest can be
easily derived. For instance, the fugacity coefficient ϕi is calculated as follows:

with

where is a partial derivative that is always done to the mole fraction


stated in the denominator, while all other mole fractions are considered
constant.

Applying ψ to the departure equations, departure functions of enthalpy,


entropy, and Gibbs free energy can be obtained as follows:
Enthalpy departure:

2 Thermodynamic Property Models 33


Entropy departure:

Gibbs free energy departure:

The following thermodynamic conditions must be satisfied:

Hard-chain Fluids and Chain Connectivity


In PC-SAFT model, a molecule is modeled as a chain molecule by a series of
freely-jointed tangent spheres. The contribution from hard-chain fluids as a
reference system consists of two parts, a nonbonding contribution (i.e., hard-
sphere mixtures prior to bonding to form chains) and a bonding contribution
due to chain formation:

where is the mean segment in the mixture, ψhs is the contribution from
hard-sphere mixtures on a per-segment basis, and ψchain is the contribution
due to chain formation. Both and ψhs are well-defined for mixtures
containing polymers, including copolymers; they are given by the following
equations:

34 2 Thermodynamic Property Models


where miα, σiα, and εiα are the segment number, the segment diameter, and
the segment energy parameter of the segment type α in the copolymer
component i, respectively. The segment number miα is calculated from the
segment ratio parameter riα:

where Miα is the total molecular weight of the segment type α in the
copolymer component i and can be calculated from the segment weight
fraction within the copolymer:

where wiα is the weight fraction of the segment type α in the copolymer
component i, and Mi is the molecular weight of the copolymer component i.
Following Sadowski and co-worker’s work (Gross et al., 2003; Becker et al.,
2004), the contribution from the chain connectivity can be written as follows:

with

where Biα,iβ is defined as the bonding fraction between the segment type α
and the segment type β within the copolymer component i, γ is the number of
the segment types within the copolymer component i, and ghsiα,jβ(diα,jβ) is the
radial distribution function of hard-sphere mixtures at contact.

However, the calculation for Biα,iβ depends on the type of copolymers. We


start with a pure copolymer system which consists of only two different types
of segments α and β; this gives:

with

2 Thermodynamic Property Models 35


We now apply these equations to three common types of copolymers; a)
alternating, b) block, and c) random.

For an alternating copolymer, mα = mβ; there are no αα or ββ adjacent


sequences. Therefore:

For a block copolymer, there is only one αβ pair and the number of αα and
ββ pairs depend on the length of each block; therefore:

For a random copolymer, the sequence is only known in a statistical sense. If


the sequence is completely random, then the number of αβ adjacent pairs is
proportional to the product of the probabilities of finding a segment of type α
and a segment of type β in the copolymer. The probability of finding a
segment of type α is the fraction of segments zα in the copolymer:

The bonding fraction of each pair of types can be written as follows:

where C is a constant and can be determined by the normalization condition


set by Equation 2.70; the value for C is unity. Therefore:

A special case is the Sadowski’s model for random copolymer with two types
of segments only (Gross et al., 2003; Becker et al., 2004). In this model, the
bonding fractions are calculated as follows:

When zβ < zα

When zα < zβ

The generalization of three common types of copolymers from two types of


different segments to multi types of different segments γ within a copolymer
is straightforward.

36 2 Thermodynamic Property Models


For a generalized alternative copolymer, mα = mβ = ... = mr = m/γ ; there
are no adjacent sequences for the same type of segments. Therefore,

For a generalized block copolymer, there is only one pair for each adjacent
type of segment pairs (α ≠ β) and the number of pairs for a same type
depends on the length of the block; therefore:

For a generalized random copolymer, the sequence is only known in a


statistical sense. If the sequence is completely random, then the number of
αβ adjacent pairs is proportional to the product of the probabilities of finding
a segment of type α and a segment of type β in the copolymer. The
probability of finding a segment of type α is the fraction of α segments zα in
the copolymer:

The bonding fraction of each pair of types can be written as follows:

where C is a constant and can be determined by the normalization condition.


Therefore,

2 Thermodynamic Property Models 37


That is,

Put C into the equation above, we obtain:

Copolymer PC-SAFT Dispersion Term


The equations for the dispersion term are given as follows:

38 2 Thermodynamic Property Models


where σiα,jβ and εiα,jβ are the cross segment diameter and energy parameters,
respectively; only one adjustable binary interaction parameter, κiα,jβ is
introduced to calculate them:

In above equations, the model constants a1i, a2i, a3i, b1i, b2i, and b3i are fitted
to pure-component vapor pressure and liquid density data of n-alkanes
(Gross and Sadowski, 2001).

Association Term for Copolymer Mixtures - 2B


Model
The association term in PC-SAFT model in general needs an iterative
procedure to calculate the fraction of a species (solvent or segment) that are
bounded to each association-site type. Only in pure or binary systems, the
fraction can be derived explicitly for some specific models. We start with
general expressions for the association contribution for copolymer systems as
follows:

where A is the association-site type index, is the association-site


number of the association-site type A on the segment type α in the
copolymer component i, and is the mole fraction of the segment type α
in the copolymer component i that are not bonded with the association-site
type A; it can be estimated as follows:

with

2 Thermodynamic Property Models 39


where is the cross effective association volume and is the
cross association energy; they are estimated via simple combination rules:

where and are the effective association volume and the


association energy between the association-site types A and B, of the
segment type α in the copolymer component i, respectively.

The association-site number of the site type A on the segment type α in the
copolymer component i is equal to the number of the segment type α in the
copolymer component i,

where Niα is the number of the segment type α in the copolymer component i
and Mα is the molecular weight of the segment type α. In other words, the
association-site number for each site type within a segment is the same;
therefore, we can rewrite the equations above as follows:

To calculate , this equation has to be solved iteratively for each


association-site type associated with a species in a component. In practice,
further assumption is needed for efficiency. The commonly used model is the
so-called 2B model (Huang and Radosz, 1990). It assumes that an associating
species (solvent or segment) has two association sites, one is designed as the
site type A and another as the site type B. Similarly to the hydrogen bonding,
type A treats as a donor site with positive charge and type B as an acceptor
site with negative charge; only the donor-acceptor association bonding is
permitted and this concept applies to both pure systems (self-association
such as water) and mixtures (both self-association and cross-association such
as water-methanol). Therefore, we can rewrite these equations as follows:

40 2 Thermodynamic Property Models


It is easy to show that

Therefore

Polar Term for Copolymer PC-SAFT


The equations for the polar term are given by Jog et al. (2001) as follows:

In the above equations, I2(η) and I3(η) are the pure fluid integrals and μiα
and (xp)iα are the dipole moment and dipolar fraction of the segment type α

within the copolymer component i, respectively. Both and

are dimensionless. In terms of them, we can have:

2 Thermodynamic Property Models 41


Rushbrooke et al. (1973) have shown that

Then I2(η) and I3(η) are computed in terms of η by the expressions:

Reference
Jog, P. K., Sauer, S. G., Blaesing, J., & Chapman, W. G. (2001), Application
of Dipolar Chain Theory to the Phase Behavior of Polar Fluids and Mixtures.
Ind. Eng. Chem. Res., 40, 4641.
Rushbrooke, G. S., & Stell, G., Hoye, J. S. (1973), Molec. Phys., 26, 1199.

Copolymer PC-SAFT EOS Model Parameters

Pure parameters
Each non-association species (solvent or segment) must have a set of three
pure-component parameter; two of them are the segment diameter σ and the
segment energy parameter ε. The third parameter for a solvent is the
segment number m and for a segment is the segment ratio parameter r. For
an association species, two additional parameters are the effective association
volume κ(AB) and the association energy ε(AB). For a polar species, two

42 2 Thermodynamic Property Models


additional parameters are the dipole moment μ and the segment dipolar
fraction xp.

Binary parameters
There are three types of binary interactions in copolymer systems: solvent-
solvent, solvent-segment, and segment-segment. The binary interaction
parameter κiα,jβ allows complex temperature dependence:

with

where Tref is a reference temperature and the default value is 298.15 K.


The following table lists the copolymer PC-SAFT EOS model parameters
implemented in Aspen Plus:
Parameter Symbol Default Lower Upper MDS Units Comments
Name/ Limit Limit Keyword
Element
PCSFTM m — — — X — Unary
PCSFTV σ — — — X — Unary
PCSFTU ε/k — — — X TEMP Unary
PCSFTR r — — — X — Unary
PCSFAU εAB/k — — — X TEMP Unary

PCSFAV κAB — — — X — Unary

PCSFMU μ — — — X DIPOLE Unary


MOMENT
PCSFXP xp — — — X — Unary
PCSKIJ/1 aiα,jβ 0.0 — — X — Binary,
Symmetric
PCSKIJ/2 biα,jβ 0.0 — — X — Binary,
Symmetric
PCSKIJ/3 ciα,jβ 0.0 — — X — Binary,
Symmetric
PCSKIJ/4 diα,jβ 0.0 — — X — Binary,
Symmetric
PCSKIJ/5 eiα,jβ 0.0 — — X — Binary,
Symmetric
PCSKIJ/6 Tref 298.15 — — X TEMP Binary,
Symmetric

2 Thermodynamic Property Models 43


Parameter Input and Regression for Copolymer
PC-SAFT
Since the copolymer PC-SAFT is built based on the segment concept, the
unary (pure) parameters must be specified for a solvent or a segment.
Specifying a unary parameter for a polymer component (homopolymer or
copolymer) will be ignored by the simulation. For a non-association and non-
polar solvent, three unary parameters PCSFTM, PCSFTU, and PCSFTV must be
specified. For a non-association and non-polar segment, these three unary
parameters PCSFTR, PCSFTU, and PCSFTV must be specified. For an
association species (solvent or segment), two additional unary parameters
PCSFAU and PCSFAV must be specified. For a polar species (solvent or
segment), two additional unary parameters PCSFMU and PCSFXP must be
specified.
The binary parameter PCSKIJ can be specified for each solvent-solvent pair,
or each solvent-segment pair, or each segment-segment pair. By default, the
binary parameter is set to be zero.
A databank called PC-SAFT contains both unary and binary PC-SAFT
parameters available from literature; it must be used with the PC-SAFT
property method. The unary parameters available for segments are stored in
the SEGMENT databank. If unary parameters are not available for a species
(solvent or segment) in a calculation, the user can perform an Aspen Plus
Data Regression Run (DRS) to obtain unary parameters. For non-polymer
components (mainly solvents), the unary parameters are usually obtained by
fitting experimental vapor pressure and liquid molar volume data. To obtain
unary parameters for a segment, experimental data on liquid density of the
homopolymer that is built by the segment should be regressed. Once the
unary parameters are available for a segment, the ideal-gas heat capacity
parameter CPIG may be regressed for the same segment using experimental
liquid heat capacity data for the same homopolymer. In addition to unary
parameters, the binary parameter PCSKIJ for each solvent-solvent pair, or
each solvent-segment pair, or each segment-segment pair, can be regressed
using vapor-liquid equilibrium (VLE) data in the form of TPXY data in Aspen
Plus.

Note: In Data Regression Run, a homopolymer must be defined as an


OLIGOMER type, and the number of the segment that builds the oligomer
must be specified.

Peng-Robinson
The Peng-Robinson equation-of-state is the basis for the PENG-ROB and PR-
BM property methods. The model has been implemented with choices of
different alpha functions (see Peng-Robinson Alpha Functions) and has been
extended to include advanced asymmetric mixing rules.

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.

44 2 Thermodynamic Property Models


By default, the PENG-ROB property method uses the literature version of the
alpha function and mixing rules. The PR-BM property method uses the
Boston-Mathias alpha function and standard mixing rules. These default
property methods are recommended for hydrocarbon processing applications
such as gas processing, refinery, and petrochemical processes. Their results
are comparable to those of the property methods that use the standard
Redlich-Kwong-Soave equation-of-state.
When advanced alpha function and asymmetric mixing rules are used with
appropriately obtained parameters, the Peng-Robinson model can be used to
accurately model polar, non-ideal chemical systems. Similar capability is also
available for the Soave-Redlich-Kwong model.
The equation for the Peng-Robinson model is:

Where:
b =

c =

a = a0+a1
a0 =

(the standard quadratic mixing term, where kij has


been made temperature-dependent)
kij =

kij = kji
a1

(an additional, asymmetric term used to model


highly non-linear systems)
lij =

In general, .
ai =

bi =

ci =

For best results, the binary parameters kij and lij must be determined from
regression of phase equilibrium data such as VLE data. The Aspen Physical

2 Thermodynamic Property Models 45


Property System also has built-in kij and lij for a large number of component
pairs in the EOS-LIT databank. These parameters are used automatically with
the PENG-ROB property method. Values in the databank can be different than
those used with other models such as Soave-Redlich-Kwong or Redlich-
Kwong-Soave, and this can produce different results.
The model has option codes which can be used to customize the model, by
selecting a different alpha function and other model options. See Peng-
Robinson Alpha Functions for a description of the alpha functions. See Option
Codes for Equation of State Models (under ESPR) for a list of the option
codes.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PRTC Tci TC x 5.0 2000.0 TEMPERATURE
5 8
PRPC pci PC x 10 10 PRESSURE
OMGPR ωi OMEGA x -0.5 2.0 —

PRZRA zRA RKTZRA x — — —


PRKBV/1 kij(1) 0 x — — —
PRKBV/2 kij(2) 0 x — — TEMPERATURE
PRKBV/3 kij(3) 0 x — — TEMPERATURE
PRKBV/4 Tlower 0 x — — TEMPERATURE
PRKBV/5 Tupper 1000 x — — TEMPERATURE
PRLIJ/1 lij(1) 0 x — — —
PRLIJ/2 lij(2) 0 x — — TEMPERATURE
PRLIJ/3 lij(3) 0 x — — TEMPERATURE
PRLIJ/4 Tlower 0 x — — TEMPERATURE
PRLIJ/5 Tupper 1000 x — — TEMPERATURE

References
D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 59–64.
P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules
for multicomponent mixtures: the problem of invariance," Fluid Phase
Equilibria, Vol 67, (1991), pp. 31-44.

Standard Peng-Robinson
The Standard Peng-Robinson equation-of-state is the original formulation of
the Peng-Robinson equation of state with the standard alpha function (see
Peng-Robinson Alpha Functions). It is recommended for hydrocarbon
processing applications such as gas processing, refinery, and petrochemical
processes. Its results are comparable to those of the standard Redlich-
Kwong-Soave equation of state.

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.

46 2 Thermodynamic Property Models


The equation for this model is:

Where:
b =

a =

ai =

bi =

kij =

The model has option codes which can be used to customize the model, by
selecting a different alpha function and other model options. See Peng-
Robinson Alpha Functions for a description of the alpha functions. See Option
Codes for Equation of State Models (under ESPRSTD) for a list of the option
codes.
For best results, the binary parameter kij must be determined from regression
of phase equilibrium data such as VLE data. The Aspen Physical Property
System also has built-in kij for a large number of component pairs in the EOS-
LIT databank. These parameters are used automatically with the PENG-ROB
property method. Values in the databank can be different than those used
with other models such as Soave-Redlich-Kwong or Redlich-Kwong-Soave,
and this can produce different results.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCPRS Tci TC x 5.0 2000.0 TEMPERATURE
PCPRS pci PC x 105 108 PRESSURE
OMGPRS ωi OMEGA x -0.5 2.0 —

PRKBV/1 kij(1) 0 x - - -
PRKBV/2 kij(2) 0 x - - TEMPERATURE
PRKBV/3 kij(3) 0 x - - TEMPERATURE
PRKBV/4 Tlower 0 x - - TEMPERATURE
PRKBV/5 Tupper 1000 x - - TEMPERATURE

References
D.-Y. Peng and D. B. Robinson, "A New Two-Constant Equation-of-state," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 59–64.

2 Thermodynamic Property Models 47


Peng-Robinson-MHV2
This model uses the Peng-Robinson equation-of-state for pure compounds.
The mixing rules are the predictive MHV2 rules. Several alpha functions can
be used in the Peng-Robinson-MHV2 equation-of-state model for a more
accurate description of the pure component behavior. The pure component
behavior and parameter requirements are described in Standard Peng-
Robinson, or in Peng-Robinson Alpha Functions.
The MHV2 mixing rules are an example of modified Huron-Vidal mixing rules.
A brief introduction is provided in Huron-Vidal Mixing Rules. For more details,
see MHV2 Mixing Rules.

Predictive SRK (PSRK)


This model uses the Redlich-Kwong-Soave equation-of-state for pure
compounds. The mixing rules are the predictive Holderbaum rules, or PSRK
method. Several alpha functions can be used in the PSRK equation-of-state
model for a more accurate description of the pure component behavior. The
pure component behavior and parameter requirements are described in
Standard Redlich-Kwong-Soave and in Soave Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The PSRK method is an example of modified Huron-Vidal mixing rules. A brief
introduction is provided in Huron-Vidal Mixing Rules. For more details, see
Predictive Soave-Redlich-Kwong-Gmehling Mixing Rules.

Peng-Robinson-Wong-Sandler
This model uses the Peng-Robinson equation-of-state for pure compounds.
The mixing rules are the predictive Wong-Sandler rules. Several alpha
functions can be used in the Peng-Robinson-Wong-Sandler equation-of-state
model for a more accurate description of the pure component behavior. The
pure component behavior and parameter requirements are described in Peng-
Robinson, and in Peng-Robinson Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The Wong-Sandler mixing rules are an example of modified Huron-Vidal
mixing rules. A brief introduction is provided in Huron-Vidal Mixing Rules. For
more details see Wong-Sandler Mixing Rules., this chapter.

48 2 Thermodynamic Property Models


Redlich-Kwong
The Redlich-Kwong equation-of-state can calculate vapor phase
thermodynamic properties for the following property methods: NRTL-RK,
UNIFAC, UNIF-LL, UNIQ-RK, VANL-RK, and WILS-RK. It is applicable for
systems at low to moderate pressures (maximum pressure 10 atm) for which
the vapor-phase nonideality is small. The Hayden-O'Connell model is
recommended for a more nonideal vapor phase, such as in systems
containing organic acids. It is not recommended for calculating liquid phase
properties.
The equation for the model is:
p =

Where:
=

b =

ai =

bi =

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TC Tci — — 5.0 2000.0 TEMPERATURE
5 8
PC pci — — 10 10 PRESSURE

References
O. Redlich and J.N.S. Kwong, "On the Thermodynamics of Solutions V. An
Equation-of-state. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44,
(1979), pp. 223 – 244.

Redlich-Kwong-Aspen
The Redlich-Kwong-Aspen equation-of-state is the basis for the RK-ASPEN
property method. It can be used for hydrocarbon processing applications. It is
also used for more polar components and mixtures of hydrocarbons, and for
light gases at medium to high pressures.
The equation is the same as Redlich-Kwong-Soave:

2 Thermodynamic Property Models 49


p =

A quadratic mixing rule is maintained for:


a =

An interaction parameter is introduced in the mixing rule for:


b =

For ai an extra polar parameter is used:


ai =

bi =

The interaction parameters are temperature-dependent:


ka,ij =

kb,ij =

For best results, binary parameters kij must be determined from phase-
equilibrium data regression, such as VLE data.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKA Tci TC x 5.0 2000.0 TEMPERATURE
PCRKA pci PC x 105 108 PRESSURE
OMGRKA ωi OMEGA x -0.5 2.0 —

RKAPOL ηi 0 x -2.0 2.0 —

RKAKA0 ka,ij0 0 x -5.0 5.0 —


RKAKA1 ka,ij1 0 x -15.0 15.0 TEMPERATURE
RKAKB0 kb,ij0 0 x -5.0 5.0 —
RKAKB1 kb,ij1 0 x -15.0 15.0 TEMPERATURE

References
Mathias, P.M., "A Versatile Phase Equilibrium Equation-of-state", Ind. Eng.
Chem. Process Des. Dev., Vol. 22, (1983), pp. 385 – 391.

Redlich-Kwong-Soave
This is the standard Redlich-Kwong-Soave equation-of-state, and is the basis
for the RK-SOAVE property method. It is recommended for hydrocarbon
processing applications, such as gas-processing, refinery, and petrochemical

50 2 Thermodynamic Property Models


processes. Its results are comparable to those of the Peng-Robinson
equation-of-state.
The equation is:

Where:

a0 is the standard quadratic mixing term:

a1 is an additional, asymmetric (polar) term:

b =

ai =

bi =

kij = kji

; ;
The parameter ai is calculated according to the standard Soave formulation
(see Soave Alpha Functions, equations 1, 2, 3, 5, and 6).

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The model uses option codes which are described in Soave-Redlich-Kwong
Option Codes.
For best results, binary parameters kij must be determined from phase-
equilibrium data regression (for example, VLE data). The Aspen Physical
Property System also has built-in kij for a large number of component pairs in
the EOS-LIT databank. These binary parameters are used automatically with
the RK-SOAVE property method. Values of kij in the databank can be different
than those used with other models such as Soave-Redlich-Kwong or Standard
Peng-Robinson, and this can produce different results.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKSS Tci TC x 5.0 2000.0 TEMPERATURE

2 Thermodynamic Property Models 51


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PCRKSS pci PC x 105 108 PRESSURE
OMRKSS ωi OMEGA x -0.5 2.0 —

RKSKBV/1 kij(1) 0 x -5.0 5.0 —


RKSKBV/2 kij(2) 0 x — — TEMPERATURE
RKSKBV/3 kij(3) 0 x — — TEMPERATURE
RKSKBV/4 Tk,lower 0 x — — TEMPERATURE
RKSKBV/5 Tk,upper 1000 x — — TEMPERATURE
RKSLBV/1 lij(1) 0 x — — —
RKSLBV/2 lij(2) 0 x — — TEMPERATURE
RKSLBV/3 lij(3) 0 x — — TEMPERATURE
RKSLBV/4 Tl,lower 0 x — — TEMPERATURE
RKSLBV/5 Tl,upper 1000 x — — TEMPERATURE

References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 – 1203.
J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures
and Temperatures by the Use of a Cubic Equation-of-state," Ind. Eng. Chem.
Res., Vol. 28, (1989), pp. 1049 – 1955.
A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich-
Kwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 7–23.

Redlich-Kwong-Soave-Boston-Mathias
The Redlich-Kwong-Soave-Boston-Mathias equation-of-state is the basis for
the RKS-BM property method. It is the Redlich-Kwong-Soave equation-of-
state with the Boston-Mathias alpha function (see Soave Alpha Functions). It
is recommended for hydrocarbon processing applications, such as gas-
processing, refinery, and petrochemical processes. Its results are comparable
to those of the Peng-Robinson-Boston-Mathias equation-of-state.

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The equation is:
p =

Where:

a0 is the standard quadratic mixing term:

52 2 Thermodynamic Property Models


a1 is an additional, asymmetric (polar) term:

b =

ai =

bi =

kij = kji

; ;
The parameter ai is calculated by the standard Soave formulation at
supercritical temperatures. If the component is supercritical, the Boston-
Mathias extrapolation is used (see Soave Alpha Functions).
The model uses option codes which are described in Soave-Redlich-Kwong
Option Codes.
For best results, binary parameters kij must be determined from phase-
equilibrium data regression (for example, VLE data).
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKS Tci TC x 5.0 2000.0 TEMPERATURE
PCRKS pci PC x 105 108 PRESSURE
OMGRKS ωi OMEGA x -0.5 2.0 —

RKSKBV/1 kij(1) 0 x -5.0 5.0 —


RKSKBV/2 kij(2) 0 x — — TEMPERATURE
RKSKBV/3 kij(3) 0 x — — TEMPERATURE
RKSKBV/4 Tk,lower 0 x — — TEMPERATURE
RKSKBV/5 Tk,upper 1000 x — — TEMPERATURE
RKSLBV/1 lij(1) 0 x — — —
RKSLBV/2 lij(2) 0 x — — TEMPERATURE
RKSLBV/3 lij(3) 0 x — — TEMPERATURE
RKSLBV/4 Tl,lower 0 x — — TEMPERATURE
RKSLBV/5 Tl,upper 1000 x — — TEMPERATURE

References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 – 1203.

2 Thermodynamic Property Models 53


Redlich-Kwong-Soave-Wong-Sandler
This equation-of-state model uses the Redlich-Kwong-Soave equation-of-state
for pure compounds. The predictive Wong-Sandler mixing rules are used.
Several alpha functions can be used in the Redlich-Kwong-Soave-Wong-
Sandler equation-of-state model for a more accurate description of the pure
component behavior. The pure component behavior and parameter
requirements are described in Standard Redlich-Kwong-Soave, and in Soave
Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The Wong-Sandler mixing rules are an example of modified Huron-Vidal
mixing rules. A brief introduction is provided in Huron-Vidal Mixing Rules. For
more details, see Wong-Sandler Mixing Rules.

Redlich-Kwong-Soave-MHV2
This equation-of-state model uses the Redlich-Kwong-Soave equation-of-state
for pure compounds. The predictive MHV2 mixing rules are used. Several
alpha functions can be used in the RK-Soave-MHV2 equation-of-state model
for a more accurate description of the pure component behavior. The pure
component behavior and its parameter requirements are described in
Standard Redlich-Kwong-Soave, and in Soave Alpha Functions.

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
The MHV2 mixing rules are an example of modified Huron-Vidal mixing rules.
A brief introduction is provided in Huron-Vidal Mixing Rules. For more details,
see MHV2 Mixing Rules.

Schwartzentruber-Renon
The Schwartzentruber-Renon equation-of-state is the basis for the SR-POLAR
property method. It can be used to model chemically nonideal systems with
the same accuracy as activity coefficient property methods, such as the
WILSON property method. This equation-of-state is recommended for highly
non-ideal systems at high temperatures and pressures, such as in methanol
synthesis and supercritical extraction applications.
The equation for the model is:
p =

Where:

54 2 Thermodynamic Property Models


a =

b =

c =

ai =

bi =

ci =

ka,ij =

lij =

kb,ij =

ka,ij = ka,ji
lij = -lji
kb,ij = kb,ji
The binary parameters ka,ij, kb,ij, and lij are temperature-dependent. In most
cases, ka,ij0 and lij0 are sufficient to represent the system of interest.
VLE calculations are independent of c. However, c does influence the fugacity
values and can be adjusted to (liquid) molar volumes. For a wide temperature
range, adjust cio to the molar volume at 298.15K or at boiling temperature.

Warning: Using c1i and c2i can cause anomalous behavior in enthalpy and
heat capacity. Their use is strongly discouraged.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKU Tci TC x 5.0 2000.0 TEMPERATURE
PCRKU pci PC x 105 108 PRESSURE
OMGRKU ωi OMEGA x -0.5 2.0 —

RKUPP0 †† q0i — x — — —
RKUPP1 †† q1i 0 x — — —
RKUPP2 †† q2i 0 x — — —
RKUC0 c0i 0 x — — —
RKUC1 c1i 0 x — — —
RKUC2 c2i 0 x — — —
RKUKA0 ††† ka,ij0 0 x — — —
RKUKA1 ††† ka,ij1 0 x — — TEMPERATURE
RKUKA2 ††† ka,ij2 0 x — — TEMPERATURE †

2 Thermodynamic Property Models 55


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
RKULA0 ††† lij0 0 x — — —
RKULA1 ††† lij1 0 x — — TEMPERATURE
RKULA2 ††† lij2 0 x — — TEMPERATURE †
RKUKB0 ††† kb,ij0 0 x — — —
RKUKB1 ††† kb,ij1 0 x — — TEMPERATURE
RKUKB2 ††† kb,ij2 0 x — — TEMPERATURE †

† Absolute temperature units are assumed for ka,ij2, lij2, and kb,ij2.
†† For polar components (dipole moment >> 0), if you do not enter q0i, the
system estimates q0i, q1i, q2i from vapor pressures using the Antoine vapor
pressure model.
††† If you do not enter at least one of the binary parameters ka,ij0, ka,ij2, lij0,
lij2, kb,ij0, or kb,ij2 the system estimates ka,ij0, ka,ij2, lij0, and lij2 from the UNIFAC
or Hayden O'Connell models.

References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 - 1203.
J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures
and Temperatures by the Use of a Cubic Equation-of-State," Ind. Eng. Chem.
Res., Vol. 28, (1989), pp. 1049 – 1955.
A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich-
Kwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 7–23.

Soave-Redlich-Kwong
The Soave-Redlich-Kwong equation-of-state is the basis of the SRK property
method. This model is based on the same equation of state as the Redlich-
Kwong-Soave model. However, this model has several important differences.
• A volume translation concept introduced by Peneloux and Rauzy is used to
improve molar liquid volume calculated from the cubic equation of state.
• Improvement in water properties is achieved by using the NBS Steam
Table.
• Improvement in speed of computation for equation based calculation is
achieved by using composition independent fugacity.
• Optional Kabadi-Danner mixing rules for improved phase equilibrium
calculations in water-hydrocarbon systems (see SRK-Kabadi-Danner)
• Optional Mathias alpha function

Note: You can choose any of the available alpha functions, but you cannot
define multiple property methods based on this model using different alpha
functions within the same run.
This equation-of-state can be used for hydrocarbon systems that include the
common light gases, such as H2S, CO2 and N2.

56 2 Thermodynamic Property Models


The form of the equation-of-state is:

Where:

a0 is the standard quadratic mixing term:

Where:

;
a1 is an additional, asymmetric (polar) term:

Where:

; ;

The enthalpy, entropy, Gibbs energy, and molar volume of water are
calculated from the steam tables. The total properties are mole-fraction
averages of these values with the properties calculated by the equation of
state for other components. Fugacity coefficient is not affected.
For best results, the binary parameter kij must be determined from phase
equilibrium data regression (for example, VLE data). The Aspen Physical
Property System also has built-in kij for a large number of component pairs in
the SRK-ASPEN databank. These parameters are used automatically with the
SRK property method. Values of kij in the databank can be different than
those used with other models such as Standard Redlich-Kwong-Soave or
Standard Redlich-Kwong-Soave, and this can produce different results.
The model uses option codes which are described in Soave-Redlich-Kwong
Option Codes.

2 Thermodynamic Property Models 57


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
SRKTC Tci TC x 5.0 2000.0 TEMPERATURE

SRKPC pci PC x 105 108 PRESSURE


SRKOMG ωi OMEGA x –0.5 2.0 —

SRKZRA zRA RKTZRA x — — —


SRKKIJ/1 kij(1) 0 x — — —
SRKKIJ/2 kij(2) 0 x — — TEMPERATURE
SRKKIJ/3 kij(3) 0 x — — TEMPERATURE
SRKKIJ/4 Tlower 0 x — — TEMPERATURE
SRKKIJ/5 Tupper 1000 x — — TEMPERATURE
SRKLIJ/1 lij(1) 0 x — — —
SRKLIJ/2 lij(2) 0 x — — TEMPERATURE
SRKLIJ/3 lij(3) 0 x — — TEMPERATURE
SRKLIJ/4 Tlower 0 x — — TEMPERATURE
SRKLIJ/5 Tupper 1000 x — — TEMPERATURE

References
G. Soave, "Equilibrium Constants for Modified Redlich-Kwong Equation-of-
state," Chem. Eng. Sci., Vol. 27, (1972), pp. 1196 - 1203.
A. Peneloux, E. Rauzy, and R. Freze, "A Consistent Correction For Redlich-
Kwong-Soave Volumes", Fluid Phase Eq., Vol. 8, (1982), pp. 7–23.
P.M. Mathias, H.C. Klotz, and J.M. Prausnitz, "Equation of state mixing rules
for multicomponent mixtures: the problem of invariance," Fluid Phase
Equilibria, Vol 67, (1991), pp. 31-44.

SRK-Kabadi-Danner
The SRK-Kabadi-Danner property model uses the SRK equation-of-state with
improved phase equilibrium calculations for mixtures containing water and
hydrocarbons. These improvements are achieved by using the Kabadi-Danner
mixing rules.
The form of the equation-of-state is:

Where:

a0 is the standard quadratic mixing term:

58 2 Thermodynamic Property Models


Where:

;
The best values of kwj (w = water) were obtained from experimental data.
Results are given for seven homologous series.

Best Fit Values of kwj for Different Homologous Series


with Water
Homologous series kwj
Alkanes 0.500
Alkenes 0.393
Dialkenes 0.311
Acetylenes 0.348
Naphthenes 0.445
Cycloalkenes 0.355
Aromatics 0.315

aKD is the Kabadi-Danner term for water:

Where:

Gi is the sum of the group contributions of different groups which make up a


molecule of hydrocarbon i.

gl is the group contribution parameter for groups constituting hydrocarbons.

Groups Constituting Hydrocarbons and Their Group


Contribution Parameters
Group l gl , atm m6 x 105
CH4 1.3580
– CH3 0.9822
– CH2 – 1.0780
> CH – 0.9728
>C< 0.8687
– CH2 – (cyclic) 0.7488
> CH – (cyclic) 0.7352
– CH = CH – (cyclic) † 0.6180

2 Thermodynamic Property Models 59


Group l gl , atm m6 x 105
CH2 = CH2 1.7940
CH2 = CH – 1.3450
CH2 = C< 0.9066
CH ≡ CH 1.6870
CH ≡ C – 1.1811
– CH = 0.5117
> C = (aromatic) 0.3902

† This value is obtained from very little data. Might not be reliable.
The model uses option codes which are described in Soave-Redlich-Kwong
Option Codes.
SRK-Kabadi-Danner uses the same parameters as SRK, with added
interaction parameters. Do not specify values for the SRKLIJ parameters
when using SRK-KD.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
SRKTC Tci TC x 5.0 2000.0 TEMPERATURE

SRKPC pci PC x 105 108 PRESSURE


SRKOMG ωi OMEGA x –0.5 2.0 —
SRKWF Gi 0 x — — —
SRKZRA zRA RKTZRA x — — —
SRKKIJ/1 kij(1) 0 x — — —
SRKKIJ/2 kij(2) 0 x — — TEMPERATURE
SRKKIJ/3 kij(3) 0 x — — TEMPERATURE
SRKKIJ/4 Tlower 0 x — — TEMPERATURE
SRKKIJ/5 Tupper 0 x — — TEMPERATURE

References
V. Kabadi and R. P. Danner, "A Modified Soave-Redlich-Kwong Equation of
State for Water-Hydrocarbon Phase Equilibria", Ind. Eng. Chem. Process Des.
Dev., Vol. 24, No. 3, (1985), pp. 537-541.

SRK-ML
The SRK-ML property model is the same as the standard Soave-Redlich-
Kwong model with two exceptions:
• kij does not equal kji for non-ideal systems; they are unsymmetric, and a
different set of parameters is used, as shown below.
• The lij are calculated from the equation lij = kji - kij

60 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
SRKTCML Tci TC x 5.0 2000.0 TEMPERATURE

SRKPCML pci PC x 105 108 PRESSURE


SRKOMGML ωi OMEGA x –0.5 2.0 —

SRKZRAML zRA RKTZRA x — — —


SRKKIJML/1 kij(1) 0 x — — —
SRKKIJML/2 kij(2) 0 x — — TEMPERATURE
SRKKIJML/3 kij(3) 0 x — — TEMPERATURE
SRKKIJML/4 Tlower 0 x — — TEMPERATURE
SRKKIJML/5 Tupper 1000 x — — TEMPERATURE

VPA/IK-CAPE Equation-of-State
The VPA/IK-CAPE equation of state is similar to the HF equation of state but
allows dimerization, tetramerization and hexamerization to occur
simultaneously. The main assumption of the model is that only molecular
association causes the gas phase nonideality. Attractive forces between the
molecules and the complexes are neglected.
There are three kinds of associations, which can be modeled:
• Dimerization (examples: formic acid, acetic acid)
• Tetramerization (example: acetic acid)
• Hexamerization (example: hydrogen fluoride)
To get the largest possible flexibility of the model all these kinds of
association can occur simultaneously, for example, in a mixture containing
acetic acid and HF. Up to five components can associate, and any number of
inert components are allowed. This is the only difference between this model
and the HF equation of state, which account only the hexamerization of HF.

Symbols
In the following description, these symbols are used:
yi = Apparent concentration
zin = True concentration, for component i and degree of
association n=1, 2, 4, 6

zMij = True concentration of cross-dimers of components i


and j, for i,j 1 to 5.
p0 = Reference pressure
k = Number of components

2 Thermodynamic Property Models 61


Association Equilibria
Every association equilibrium reaction
(1)

(2)

is described by the equilibrium constants


(3)

(4)

By setting
(5)

(6)

their temperature dependence can be reproduced.


To evaluate the true concentration of every complex zin, the following
nonlinear systems of equations are to be solved:
Total mass balance:
The sum of true concentrations is unity.

(7)

Mass balance for every component i>1:


The ratio of the monomers of each component i>1 and component i=1
occurring in the various complexes must be equal to the ratio of their
apparent concentrations.

(8)

Thus, a system of k nonlinear equations for k unknowns zi1 has been


developed. After having solved it, all the zin and zMij can be determined using

62 2 Thermodynamic Property Models


equations (3, 4). This is the main step to evaluate all the properties needed
for a calculation.

Specific Volume of the Gas Phase


The compressibility factor is defined by the ratio between the number of
complexes and the number of monomers in the complexes.

(9)

The compressibility factor itself is


(10)

Fugacity Coefficient
As is well-known from thermodynamics, the fugacity coefficient can be
calculated by
(11)

Isothermal Enthalpy Departure


According to the ASPEN enthalpy model, an equation of state must supply an
expression to compute the isothermal molar enthalpy departure between zero
pressure and actual pressure. In the following section this enthalpy
contribution per mole monomers is abbreviated by Δha.
Taking this sort of gas phase non-ideality into account, the specific enthalpy
per mole can be written as
(12)

with
(13)

to evaluate Δha, a mixture consisting of N monomers integrated in the


complexes is considered. The quota of monomers i being integrated in a
complex of degree n is given by

2 Thermodynamic Property Models 63


(14)

and
(16)

respectively. For the reactions mentioned above:


(1)

(2)

the enthalpies of reaction are


(17)

(18)

as the van't Hoff equation


(19)

holds for this case.


For each monomer being integrated in a complex of degree n, its contribution
to the enthalpy departure is Δhin / n or ΔhMij / 2, respectively. Hence, Δha can
easily be derived by

(20)

Isothermal entropy and Gibbs energy departure:


A similar expression for Δga should hold as it does for the enthalpy departure
(eq. 20):
(21)

64 2 Thermodynamic Property Models


using
(22)

and
(23)

(24)

Using the association model, more different species occur than can be
distinguished. Thus, the equivalent expression for the entropy of mixing
should be written with the true concentrations. As eq. 24 refers to 1 mole
monomers, the expression should be weighted by the compressibility factor
representing the true number of moles. The new expression is
(25)

For Δga we obtain


(26)

and, analogously,
(27)

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
DMER/1 Ai2 0 X – – –
DMER/2 Bi2 0 X – – TEMPERATURE
TMER/1 Ai4 0 X – – –
TMER/2 Bi4 0 X – – TEMPERATURE
HMER/1 Ai6 0 X – – –
HMER/2 Bi6 0 X – – TEMPERATURE

References
M. M. Abbott and H. C. van Ness, "Thermodynamics of Solutions Containing
Reactive Species, a Guide to Fundamentals and Applications," Fluid Phase Eq.,
Vol. 77, (1992) pp. 53–119.
V. V. De Leeuw and S. Watanasiri, "Modeling Phase Equilibria and Enthalpies
of the System Water and Hydrofluoric Acid Using an HF Equation-of-state in
Conjunction with the Electrolyte NRTL Activity Coefficient Model," Paper
Presented at the 13th European Seminar on Applied Thermodynamics, June
9–12, Carry-le-Rouet, France, 1993.

2 Thermodynamic Property Models 65


R. W. Long, J. H. Hildebrand, and W. E. Morrell, "The Polymerization of
Gaseous Hydrogen and Deuterium Fluorides," J. Am. Chem. Soc., Vol. 65,
(1943), pp. 182–187.
C. E. Vanderzee and W. Wm. Rodenburg, "Gas Imperfections and
Thermodynamic Excess Properties of Gaseous Hydrogen Fluoride," J. Chem.
Thermodynamics, Vol. 2, (1970), pp. 461–478.

Peng-Robinson Alpha Functions


The pure component parameters for the Peng-Robinson equation-of-state are
calculated as follows:
(1)

(2)

These expressions are derived by applying the critical constraints to the


equation-of-state under these conditions:
(3)

The parameter α is a temperature function. It was originally introduced by


Soave in the Redlich-Kwong equation-of-state. This parameter improves the
correlation of the pure component vapor pressure.

Note: You can choose any of the alpha functions described here, but you
cannot define multiple property methods based on this model using different
alpha functions within the same run.
This approach was also adopted by Peng and Robinson:
(4)

Equation 3 is still represented. The parameter mi can be correlated with the


acentric factor:
(5)

Equations 1 through 5 are the standard Peng-Robinson formulation. The


Peng-Robinson alpha function is adequate for hydrocarbons and other
nonpolar compounds, but is not sufficiently accurate for polar compounds.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCPR Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCPR pci PC X 10 10 PRESSURE
OMGPR ωi OMEGA X -0.5 2.0 —

66 2 Thermodynamic Property Models


Boston-Mathias Extrapolation
For light gases at high reduced temperatures (> 5), equation 4 gives
unrealistic results. The boundary conditions are that attraction between
molecules should vanish for extremely high temperatures, and α reduces
asymptotically to zero. Boston and Mathias derived an alternative function for
temperatures higher than critical:
(6)

With
=

Where mi is computed by equation 5, and equation 4 is used for subcritical


temperatures. Additional parameters are not needed.

Extended Gibbons-Laughton Alpha Function


The extended Gibbons-Laughton alpha function is suitable for use with both
polar and nonpolar components. It has the flexibility to fit the vapor pressure
of most substances from the triple point to the critical point.

Where Tr is the reduced temperature; Xi, Yi and Zi are substance dependent


parameters.
This function is equivalent to the standard Peng-Robinson alpha function if

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
PRGLP/1 X — X — — —
PRGLP/2 Y 0 X — — —
PRGLP/3 Z 0 X — — —
PRGLP/4 n 2 X — — —
PRGLP/5 Tlower 0 X — — TEMPERATURE
PRGLP/6 Tupper 1000 X — — TEMPERATURE

Twu Generalized Alpha Function


The Twu generalized alpha function is a theoretically-based function that is
currently recognized as the best available alpha function. It behaves better
than other functions at supercritical conditions (T > Tc) and when the acentric
factor is large. The improved behavior at high values of acentric factor is
important for high molecular weight pseudocomponents. There is no limit on
the minimum value of acentric factor that can be used with this function.

2 Thermodynamic Property Models 67


Where the L, M, and N are parameters that vary depending on the equation of
state and whether the temperature is above or below the critical temperature
of the component.
For Peng-Robinson equation of state:
Subcritical T Supercritical T
L(0) 0.272838 0.373949
(0)
M 0.924779 4.73020
(0)
N 1.19764 -0.200000
(1)
L 0.625701 0.0239035
M(1) 0.792014 1.24615
(1)
N 2.46022 -8.000000

Twu Alpha Function


The Twu alpha function is a theoretically-based function that is currently
recognized as the best available alpha function. It behaves better than other
functions at supercritical conditions (T > Tc).

Where the L, M, and N are substance-dependent parameters that must be


determined from regression of pure-component vapor pressure data or other
data such as liquid heat capacity.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PRTWUP/1 L — X — — —
PRTWUP/2 M 0 X — — —
PRTWUP/3 N 0 X — — —

Mathias-Copeman Alpha Function


This is an extension of the Peng-Robinson alpha function which provides a
more accurate fit of vapor pressure for polar compounds.
(7)

For c2,i = 0 and c3,i = 0, this expression reduces to the standard Peng-
Robinson formulation if c2,i = mi. You can use vapor pressure data if the
temperature is subcritical to regress the constants. If the temperature is
supercritical, c2,i and c3,i are set to 0.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCPR Tci TC X 5.0 2000.0 TEMPERATURE
PCPR pci PC X 105 108 PRESSURE

68 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PRMCP/1 c1,i — X — — —
PRMCP/2 c2,i 0 X — — —
PRMCP/3 c3,i 0 X — — —

Schwartzentruber-Renon-Watanasiri Alpha Function


The Schwartzentruber-Renon-Watanasiri alpha function is:
(8)

Where mi is computed by equation 5. The polar parameters p1,i, p2,i and p3,i
are comparable with the c parameters of the Mathias-Copeman expression.
Equation 8 reduces to the standard Peng-Robinson formulation if the polar
parameters are zero. Equation 8 is used only for below-critical temperatures.
For above-critical temperatures, the Boston-Mathias extrapolation is used.
Use equation 6 with:
(9)

(10)

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TCPR Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCPR pci PC X 10 10 PRESSURE
OMGPR ωi OMEGA X -0.5 2.0 —

PRSRP/1 — X — — —

PRSRP/2 0 X — — —

PRSRP/3 0 X — — —

Use of Alpha Functions


The alpha functions in Peng-Robinson-based equation-of-state models is
provided in the following table. You can verify and change the value of
possible option codes on the Properties | Property Methods | Model form.
Alpha function Model name First Option code
Standard Peng Robinson ESPRSTD0, ESPRSTD 1
Standard PR/ ESPR0, ESPR 0
Boston-Mathias ESPRWS0, ESPRWS 0
ESPRV20, ESPRV2 0
Extended Gibbons- ESPR0, ESPR 2
Laughton
Twu Generalized alpha ESPR0, ESPR 3
function
Twu alpha function ESPR0, ESPR 4

2 Thermodynamic Property Models 69


Alpha function Model name First Option code
Mathias-Copeman ESPRWS0, ESPRWS 2
ESPRV20, ESPRV2 2
Schwartzentruber- ESPRWS0, ESPRWS 3 (default)
Renon- ESPRV20, ESPRV2 3 (default)
Watanasiri

References
J. F. Boston and P.M. Mathias, "Phase Equilibria in a Third-Generation Process
Simulator" in Proceedings of the 2nd International Conference on Phase
Equilibria and Fluid Properties in the Chemical Process Industries, West Berlin,
(17-21 March 1980) pp. 823-849.
D.-Y. Peng and D.B. Robinson, "A New Two-Constant Equation-of-state," Ind.
Eng. Chem. Fundam., Vol. 15, (1976), pp. 59-64.
P.M. Mathias and T.W. Copeman, "Extension of the Peng-Robinson Equation-
of-state To Complex Mixtures: Evaluation of the Various Forms of the Local
Composition Concept",Fluid Phase Eq., Vol. 13, (1983), p. 91.
J. Schwartzentruber, H. Renon, and S. Watanasiri, "K-values for Non-Ideal
Systems:An Easier Way," Chem. Eng., March 1990, pp. 118-124.
G. Soave, "Equilibrium Constants for a Modified Redlich-Kwong Equation-of-
state," Chem Eng. Sci., Vol. 27, (1972), pp. 1196-1203.
C.H. Twu, J. E. Coon, and J.R. Cunningham, "A New Cubic Equation of State,"
Fluid Phase Equilib., Vol. 75, (1992), pp. 65-79.
C.H. Twu, D. Bluck, J.R. Cunningham, and J.E. Coon, "A Cubic Equation of
State with a New Alpha Function and a New Mixing Rule," Fluid Phase Equilib.,
Vol. 69, (1991), pp. 33-50.

Soave Alpha Functions


The pure component parameters for the Redlich-Kwong equation-of-state are
calculated as:
(1)

(2)

These expressions are derived by applying the critical constraint to the


equation-of-state under these conditions:
(3)

Note: You can choose any of the alpha functions described here, but you
cannot define multiple property methods based on this model using different
alpha functions within the same run.
In the Redlich-Kwong equation-of-state, alpha is:

70 2 Thermodynamic Property Models


(4)

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TC Tci — — 5.0 2000.0 TEMPERATURE
PC pci — — 105 108 PRESSURE

Soave Modification
The parameter αi is a temperature function introduced by Soave in the
Redlich-Kwong equation-of-state to improve the correlation of the pure
component vapor pressure:
(5)

Equation 3 still holds. The parameter mi can be correlated with the acentric
factor:
(6)

Equations 1, 2, 3, 5 and 6 are the standard Redlich-Kwong-Soave


formulation. The Soave alpha function is adequate for hydrocarbons and other
nonpolar compounds, but is not sufficiently accurate for polar compounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKS Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCRKS pci PC X 10 10 PRESSURE
OMGRKS ωi OMEGA X -0.5 2.0 —

Boston-Mathias Extrapolation
For light gases at high reduced temperatures (> 5), equation 5 gives
unrealistic results. The boundary conditions are that attraction between
molecules should vanish for extremely high temperatures, and reduces
asymptotically to zero. Boston and Mathias derived an alternative function for
temperatures higher than critical:
(7)

With
di =

ci =

Where:

2 Thermodynamic Property Models 71


mi = Computed by equation 6
Equation 5 = Used for subcritical temperatures
Additional parameters are not needed.

Mathias Alpha Function


This is an extension of the Soave alpha function which provides a more
accurate fit of vapor pressure for polar compounds.
(8)

For ηi=0, equation 8 reduces to the standard Redlich-Kwong-Soave


formulation, equations 5 and 6. For temperatures above critical, the Boston-
Mathias extrapolation is used, that is, equation 7 with:
(9)

(10)

The Mathias alpha function is used in the Redlich-Kwong-Aspen model, which


is the basis for the RK-ASPEN property method. This alpha function is also
available as an option for SRK, SRKKD, SRK-ML, RK-SOAVE, and RKS-BM.
See Soave-Redlich-Kwong Option Codes for more information.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKA Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCRKA pci PC X 10 10 PRESSURE
OMGRKA ωi OMEGA X -0.5 2.0 —
† ηi — X -2.0 2.0 —

† RKAPOL for Redlich-Kwong-Aspen, SRKPOL for SRK and SRKKD, SRKMLP for
SRK-ML, RKSPOL for RKS-BM, or RKSSPO for RK-SOAVE.

Extended Mathias Alpha Function


An extension of the Mathias approach is:
(11)

Where mi is computed by equation 6. If the polar parameters p1,i, p2,i and p3,i
are zero, equation 11 reduces to the standard Redlich-Kwong-Soave
formulation. You can use vapor pressure data to regress the constants if the
temperature is subcritical. Equation 11 is used only for temperatures below
critical.
The Boston-Mathias extrapolation is used for temperatures above critical, that
is, with:
(12)

72 2 Thermodynamic Property Models


(13)

This alpha function is used in the Redlich-Kwong-UNIFAC model which is the


basis for the SR-POLAR property method.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKU Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCRKU pci PC X 10 10 PRESSURE
OMGRKU ωi OMEGA X -0.5 2.0 —
RKUPP0 p1,i — X — — —
RKUPP1 p2,i 0 X — — —
RKUPP2 p3,i 0 X — — —

Mathias-Copeman Alpha Function


The Mathias-Copeman alpha function is suitable for use with both polar and
nonpolar components. It has the flexibility to fit the vapor pressure of most
substances from the triple point to the critical point.
(14)

For c2,i=0 and c3,i=0 this expression reduces to the standard Redlich-Kwong-
Soave formulation if c1,i=mi. If the temperature is subcritical, use vapor
pressure data to regress the constants. If the temperature is supercritical, set
c2,i and c3,i to 0.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCRKS Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCRKS pci PC X 10 10 PRESSURE
RKSMCP/1 c1,i — X — — —
RKSMCP/2 c2,i 0 X — — —
RKSMCP/3 c3,i 0 X — — —

Schwartzentruber-Renon-Watanasiri Alpha Function


The Schwartzentruber-Renon-Watanasiri alpha function is:
(15)

Where mi is computed by equation 6 and the polar parameters p1,i, p2,i and p3,i
are comparable with the c parameters of the Mathias-Copeman expression.
Equation 15 reduces to the standard Redlich-Kwong-Soave formulation if the
polar parameters are zero. Equation 15 is very similar to the extended
Mathias equation, but it is easier to use in data regression. It is used only for
temperatures below critical. The Boston-Mathias extrapolation is used for
temperatures above critical, that is, use equation 7 with:
(16)

2 Thermodynamic Property Models 73


(17)

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TCRKS Tci TC X 5.0 2000.0 TEMPERATURE
5 8
PCRKS pci PC X 10 10 PRESSURE
OMGRKS ωi OMEGA X -0.5 2.0 —
RKSSRP/1 p1,i — X — — —
RKSSRP/2 p2,i 0 X — — —
RKSSRP/3 p3,i 0 X — — —

Extended Gibbons-Laughton Alpha Function


The extended Gibbons-Laughton alpha function is suitable for use with both
polar and nonpolar components. It has the flexibility to fit the vapor pressure
of most substances from the triple point to the critical point.

Where Tr is the reduced temperature; Xi, Yi and Zi are substance dependent


parameters.
This function is equivalent to the standard Soave alpha function if

This function is not intended for use in supercritical conditions. To avoid


predicting negative alpha, when Tri>1 the Boston-Mathias alpha function is
used instead.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
RKSGLP/1 X — X — — —
RKSGLP/2 Y 0 X — — —
RKSGLP/3 Z 0 X — — —
RKSGLP/4 n 2 X — — —
RKSGLP/5 Tlower 0 X — — TEMPERATURE
RKSGLP/6 Tupper 1000 X — — TEMPERATURE

Twu Generalized Alpha Function


The Twu generalized alpha function is a theoretically-based function that is
currently recognized as the best available alpha function. It behaves better
than other functions at supercritical conditions (T > Tc) and when the acentric
factor is large. The improved behavior at high values of acentric factor is
important for high molecular weight pseudocomponents. There is no limit on
the minimum value of acentric factor that can be used with this function.

74 2 Thermodynamic Property Models


Where the L, M, and N are parameters that vary depending on the equation of
state and whether the temperature is above or below the critical temperature
of the component.
For Soave-Redlich-Kwong:
Subcritical T Supercritical T
L(0) 0.544000 0.379919
(0)
M 1.01309 5.67342
(0)
N 0.935995 -0.200000
(1)
L 0.544306 0.0319134
M(1) 0.802404 1.28756
(1)
N 3.10835 -8.000000

Use of Alpha Functions


The use of alpha functions in Soave-Redlich-Kwong based equation-of-state
models is given in the following table. You can verify and change the value of
possible option codes on the Properties | Property Methods | Models
sheet.
Alpha Function Model Name First Option Code
original RK ESRK0, ESRK —
standard RKS ESRKSTD0, ESRKSTD —
* 1, 2 (default)
standard RKS/Boston-Mathias * 0
ESRKSWS0, ESRKSWS 1
ESRKSV10, ESRKV1 1
ESRKSV20, ESRKSV2 1
Mathias/Boston-Mathias ESRKA0, ESRKA —
Extended Mathias/Boston- ESRKU0, ESRKU —
Mathias
Mathias-Copeman ESRKSV10, ESRKSV1 2
ESRKSV20, ESRKSV2 2
Schwartzentruber-Renon- ESPRWS0, ESPRWS 3 (default)
Watanasiri ESRKSV10, ESRKSV1 3 (default)
ESRKSV20, ESRKSV2 3 (default)
Twu generalized * 5
Gibbons-Laughton with Patel * 3
extension
Mathias for T < Tc; Boston- * 4
Mathias for T > Tc

* ESRKSTD0, ESRKSTD, ESRKS0, ESRKS, ESSRK, ESSRK0, ESRKSML,


ESRKSML0. The default alpha function (option code 2) for these models is the

2 Thermodynamic Property Models 75


standard RKS alpha function, except that the Grabovsky-Daubert alpha
function is used for H2: α = 1.202 exp(-0.30228xTri)

References
J. F. Boston and P.M. Mathias, "Phase Equilibria in a Third-Generation Process
Simulator" in Proceedings of the 2nd International Conference on Phase
Equilibria and Fluid Properties in the Chemical Process Industries, West Berlin,
(17-21 March 1980), pp. 823-849.
P. M. Mathias, "A Versatile Phase Equilibrium Equation-of-state", Ind. Eng.
Chem. Process Des. Dev., Vol. 22, (1983), pp. 385–391.
P.M. Mathias and T.W. Copeman, "Extension of the Peng-Robinson Equation-
of-state To Complex Mixtures: Evaluation of the Various Forms of the Local
Composition Concept", Fluid Phase Eq., Vol. 13, (1983), p. 91.
O. Redlich and J. N. S. Kwong, "On the Thermodynamics of Solutions V. An
Equation-of-state. Fugacities of Gaseous Solutions," Chem. Rev., Vol. 44,
(1949), pp. 223–244.
J. Schwartzentruber and H. Renon, "Extension of UNIFAC to High Pressures
and Temperatures by the Use of a Cubic Equation-of-state," Ind. Eng. Chem.
Res., Vol. 28, (1989), pp. 1049–1055.
J. Schwartzentruber, H. Renon, and S. Watanasiri, "K-values for Non-Ideal
Systems:An Easier Way," Chem. Eng., March 1990, pp. 118-124.
G. Soave, "Equilibrium Constants for a Modified Redlich-Kwong Equation-of-
state," Chem Eng. Sci., Vol. 27, (1972), pp. 1196-1203.
C.H. Twu, W.D. Sim, and V. Tassone, "Getting a Handle on Advanced Cubic
Equations of State", Chemical Engineering Progress, Vol. 98 #11 (November
2002) pp. 58-65.

Huron-Vidal Mixing Rules


Huron and Vidal (1979) used a simple thermodynamic relationship to equate
the excess Gibbs energy to expressions for the fugacity coefficient as
computed by equations of state:
(1)

Equation 1 is valid at any pressure, but cannot be evaluated unless some


assumptions are made. If Equation 1 is evaluated at infinite pressure, the
mixture must be liquid-like and extremely dense. It can be assumed that:
(2)

(3)

Using equations 2 and 3 in equation 1 results in an expression for a/b that


contains the excess Gibbs energy at an infinite pressure:

76 2 Thermodynamic Property Models


(4)

Where:
(5)

The parameters λ1and λ2depend on the equation-of-state used. In general a


cubic equation-of-state can be written as:
(6)

Values for λ1and λ2 for the Peng-Robinson and the Soave-Redlich-Kwong


equations of state are:
Equation-of-state λ1 λ2
Peng-Robinson

Redlich-Kwong-Soave 1 0

This expression can be used at any pressure as a mixing rule for the
parameter. The mixing rule for b is fixed by equation 3. Even when used at
other pressures, this expression contains the excess Gibbs energy at infinite
pressure. You can use any activity coeffecient model to evaluate the excess
Gibbs energy at infinite pressure. Binary interaction coefficients must be
regressed. The mixing rule used contains as many binary parameters as the
activity coefficient model chosen.
This mixing rule has been used successfully for polar mixtures at high
pressures, such as systems containing light gases. In theory, any activity
coefficient model can be used. But the NRTL equation (as modified by Huron
and Vidal) has demonstrated better performance.
The Huron-Vidal mixing rules combine extreme flexibility with thermodynamic
consistency, unlike many other mole-fraction-dependent equation-of-state
mixing rules. The Huron-Vidal mixing rules do not allow flexibility in the
description of the excess molar volume, but always predict reasonable excess
volumes.
The Huron-Vidal mixing rules are theoretically incorrect for low pressure,
because quadratic mole fraction dependence of the second virial coefficient (if
derived from the equation-of-state) is not preserved. Since equations of state
are primarily used at high pressure, the practical consequences of this
drawback are minimal.
The Gibbs energy at infinite pressure and the Gibbs energy at an arbitrary
high pressure are similar. But the correspondence is not close enough to
make the mixing rule predictive.
There are several methods for modifying the Huron-Vidal mixing rule to make
it more predictive. The following three methods are used in Aspen Physical
Property System equation-of-state models:

2 Thermodynamic Property Models 77


• The modified Huron-Vidal mixing rule, second order approximation
(MHV2)
• The Predictive SRK Method (PSRK)
• The Wong-Sandler modified Huron-Vidal mixing rule (WS)
These mixing rules are discussed separately in the following sections. They
have major advantages over other composition-dependent equation-of-state
mixing rules.

References
M.- J. Huron and J. Vidal, "New Mixing Rules in Simple Equations of State for
representing Vapour-liquid equilibria of strongly non-ideal mixtures," Fluid
Phase Eq., Vol. 3, (1979), pp. 255-271.

MHV2 Mixing Rules


Dahl and Michelsen (1990) use a thermodynamic relationship between excess
Gibbs energy and the fugacity computed by equations of state. This
relationship is equivalent to the one used by Huron and Vidal:
(1)

The advantage is that the expressions for mixture and pure component
fugacities do not contain the pressure. They are functions of compacity V/b
and α:
(2)

Where:
(3)

and
(4)

With:
(5)

The constants λ1 and λ2, which depend only on the equation-of-state (see
Huron-Vidal Mixing Rules) occur in equations 2 and 4.
Instead of using infinite pressure for simplification of equation 1, the condition
of zero pressure is used. At p = 0 an exact relationship between the

78 2 Thermodynamic Property Models


compacity and α can be derived. By substitution the simplified equation q(α)
is obtained, and equation 1 becomes:
(6)

However, q(α) can only be written explicitly for α = 5.8. Only an


approximation is possible below that threshold. Dahl and Michelsen use a
second order polynomial fitted to the analytical solution for 10 < α < 13 that
can be extrapolated to low alpha:
(7)

Since q(α)is a universal function (for each equation-of-state), the


combination of equations 6 and 7 form the MHV2 mixing rule. Excess Gibbs
energies, from any activity coefficient model with parameters optimized at
low pressures, can be used to determine α, if αi, bi, and b are known. To
compute b, a linear mixing rule is assumed as in the original Huron-Vidal
mixing rules:
(8)

This equation is equivalent to the assumption of zero excess molar volume.


The MHV2 mixing rule was the first successful predictive mixing rule for
equations of state. This mixing rule uses previously determined activity
coefficient parameters for predictions at high pressures. UNIFAC was chosen
as a default for its predictive character. The Lyngby modified UNIFAC
formulation was chosen for optimum performance (see UNIFAC (Lyngby
Modified)). However, any activity coefficient model can be used when its
binary interaction parameters are known.
Like the Huron-Vidal mixing rules, the MHV2 mixing rules are not flexible in
the description of the excess molar volume. The MHV2 mixing rules are
theoretically incorrect at the low pressure limit. But the practical
consequences of this drawback are minimal (see Huron-Vidal Mixing Rules,
this chapter).
Reference: S. Dahl and M.L. Michelsen, "High-Pressure Vapor-Liquid
Equilibrium with a UNIFAC-based Equation-of-state," AIChE J., Vol. 36,
(1990), pp. 1829-1836.

Predictive Soave-Redlich-Kwong-Gmehling
Mixing Rules
These mixing rules by Holderbaum and Gmehling (1991) use a relationship
between the excess Helmholtz energy and equation-of-state. They do not use
a relationship between equation-of-state properties and excess Gibbs energy,
as in the Huron-Vidal mixing rules. The pressure-explicit expression for the
equation-of-state is substituted in the thermodynamic equation:

2 Thermodynamic Property Models 79


(1)

The Helmholtz energy is calculated by integration. AE is obtained by:


(2)

Where both Ai* and Am are calculated by using equation 1. Ai* and Am are
written in terms of equation-of-state parameters.
The simplification of constant packing fraction (Vm / b) is used:
(3)

With:
(4)

Therefore:
(5)

The mixing rule is:


(6)

Where Λ' is slightly different from Λ for the Huron-Vidal mixing rule:
(7)

Where λ1 and λ2, depend on the equation-of-state (see Huron-Vidal Mixing


Rules). If equation 6 is applied at infinite pressure, the packing fraction goes
to 1. The excess Helmholtz energy is equal to the excess Gibbs energy. The
Huron-Vidal mixing rules are recovered.
The goal of these mixing rules is to be able to use binary interaction
parameters for activity coefficient models at any pressure. These parameters
have been optimized at low pressures. UNIFAC is chosen for its predictive
character. Two issues exist: the packing fraction is not equal to one, and the
excess Gibbs and Helmholtz energy are not equal at the low pressure where
the UNIFAC parameters have been derived.
Fischer (1993) determined that boiling point, the average packing fraction for
about 80 different liquids with different chemical natures was 1.1. Adopting
this value, the difference between liquid excess Gibbs energy and liquid
excess Helmholtz energy can be computed as:

80 2 Thermodynamic Property Models


(8)

The result is a predictive mixing rule for cubic equations of state. But the
original UNIFAC formulation gives the best performance for any binary pair
with interactions available from UNIFAC. Gas-solvent interactions are
unavailable.
At the University of Oldenburg in Germany, the UNIFAC groups were
extended with often-occurring gases. New group interactions were
determined from gas-solvent data, specific to the Redlich-Kwong-Soave
equation-of-state. The new built-in parameters to the Aspen Physical Property
System are activated when using the PSRK equation-of-state model.
The PSRK method has a lot in common with the Huron-Vidal mixing rules. The
mole fraction is dependent on the second virial coefficient and excess volume
is predicted. These are minor disadvantages.

References
K. Fischer, "Die PSRK-Methode: Eine Zustandsgleichung unter Verwendung
des UNIFAC-Gruppenbeitragsmodells," (Düsseldorf: VDI Fortschrittberichte,
Reihe 3: Verfahrenstechnik, Nr. 324, VDI Verlag GmbH, 1993).
T. Holderbaum and J. Gmehling, "PSRK: A Group Contribution Equation-of-
state based on UNIFAC," Fluid Phase Eq., Vol. 70, (1991), pp. 251-265.

Wong-Sandler Mixing Rules


These mixing rules use a relationship between the excess Helmholtz energy
and equation-of-state. They do not use a relationship between equation-of-
state properties and excess Gibbs energy, as in the Huron-Vidal mixing rules.
The pressure-explicit expression for the equation-of-state is substituted in the
thermodynamic equation:
(1)

The Helmholtz energy is obtained by integration, AE is obtained by:


(2)

Where both Ai* and Am are calculated by using equation 1. Ai* and Am are
written in terms of equation-of-state parameters.
Like Huron and Vidal, the limiting case of infinite pressure is used. This
simplifies the expressions for Ai* and Am. Equation 2 becomes:
(3)

Where Λ depends on the equation-of-state (see Huron-Vidal Mixing Rules).

2 Thermodynamic Property Models 81


Equation 3 is completely analogous to the Huron-Vidal mixing rule for the
excess Gibbs energy at infinite pressure. (See equation 4, Huron-Vidal Mixing
Rules.) The excess Helmholtz energy can be approximated by the excess
Gibbs energy at low pressure from any liquid activity coefficient model. Using
the Helmholtz energy permits another mixing rule for b than the linear mixing
rule. The mixing rule for b is derived as follows. The second virial coefficient
must depend quadratically on the mole fraction:
(4)

With:
(5)

The relationship between the equation-of-state at low pressure and the virial
coefficient is:
(6)

(7)

Wong and Sandler discovered the following mixing rule to satisfy equation 4
(using equations 6 and 7):

The excess Helmholtz energy is almost independent of pressure. It can be


approximated by the Gibbs energy at low pressure. The difference between
the two functions is corrected by fitting kij until the excess Gibbs energy from
the equation-of-state (using the mixing rules 3 and 8) is equal to the excess
Gibbs energy computed by an activity coeffecient model. This is done at a
specific mole fraction and temperature.
This mixing rule accurately predicts the VLE of polar mixtures at high
pressures. UNIFAC or other activity coeffecient models and parameters from
the literature are used. Gas solubilities are not predicted. They must be
regressed from experimental data.
Unlike other (modified) Huron-Vidal mixing rules, the Wong and Sandler
mixing rule meets the theoretical limit at low pressure. The use of kij does
influence excess molar volume behavior. For calculations where densities are
important, check whether they are realistic.

References
D. S. Wong and S. I. Sandler, "A Theoretically Correct New Mixing Rule for
Cubic Equations of State for Both Highly and Slightly Non-ideal Mixtures,"
AIChE J., Vol. 38, (1992), pp. 671 – 680.

82 2 Thermodynamic Property Models


D. S. Wong, H. Orbey, and S. I. Sandler, "Equation-of-state Mixing Rule for
Non-ideal Mixtures Using Available Activity Coefficient Model Parameters and
That Allows Extrapolation over Large Ranges of Temperature and Pressure",
Ind Eng Chem. Res., Vol. 31, (1992), pp. 2033 – 2039.
H. Orbey, S. I. Sandler and D. S. Wong, "Accurate Equation-of-state
Predictions at High Temperatures and Pressures Using the Existing UNIFAC
Model," Fluid Phase Eq., Vol. 85, (1993), pp. 41 – 54.

Activity Coefficient Models


The Aspen Physical Property System has the following built-in activity
coefficient models. This section describes the activity coefficient models
available.
Model Type
Bromley-Pitzer Electrolyte
Chien-Null Regular solution, local composition
Constant Activity Coefficient Arithmetic
COSMO-SAC Regular solution
Electrolyte NRTL Electrolyte
ENRTL-SAC Segment contribution, electrolyte
Hansen Regular solution
Ideal Liquid Ideal
NRTL (Non-Random-Two-Liquid) Local composition
NRTL-SAC Segment contribution
Pitzer Electrolyte
Polynomial Activity Coefficient Arithmetic
Redlich-Kister Arithmetic
Scatchard-Hildebrand Regular solution
Three-Suffix Margules Arithmetic
UNIFAC Group contribution
UNIFAC (Lyngby modified) Group contribution
UNIFAC (Dortmund modified) Group contribution
UNIQUAC Local composition
Van Laar Regular solution
Wagner interaction parameter Arithmetic
Wilson Local composition
Wilson with Liquid Molar Volume Local composition

Bromley-Pitzer Activity Coefficient Model


The Bromley-Pitzer activity coefficient model is a simplified Pitzer activity
coefficient model with Bromley correlations for the interaction parameters.
See Working Equations for a detailed description. This model has predictive

2 Thermodynamic Property Models 83


capabilities. It can be used to compute activity coefficients for aqueous
electrolytes up to 6 molal ionic strength, but is less accurate than the Pitzer
model if the parameter correlations are used. The model should not be used
for mixed-solvent electrolyte systems.
The Bromley-Pitzer model in the Aspen Physical Property System involves
user-supplied parameters, used in the calculation of binary parameters for the
electrolyte system.

Parameters β(0), β(1), β(2), β(3), and θ have five elements to account for
temperature dependencies. Elements P1 through P5 follow the temperature
dependency relation:

Where:
Tref = 298.15K
The user must:
• Supply these elements using a Properties Parameters Binary T-Dependent
form.
• Specify Comp ID i and Comp ID j on this form, using the same order that
appears on the Components Specifications Selection sheet form.
Parameter Name Symbol No. of Elements Default Units
Ionic Unary Parameters
GMBPB βion 1 0 —

GMBPD δion 1 0 —
Cation-Anion Parameters
GMBPB0 β(0) 5 0 —

GMBPB1 β(1) 5 0 —

GMBPB2 β(2) 5 0 —

GMBPB3 β(3) 5 0 —
Cation-Cation Parameters
GMBPTH θcc' 5 0 —
Anion-Anion Parameters
GMBPTH θaa' 5 0 —
Molecule-Ion and Molecule-Molecule Parameters
GMBPB0 β(0) 5 0 —

GMBPB1 β(1) 5 0 —

Working Equations
The complete Pitzer equation (Fürst and Renon, 1982) for the excess Gibbs
energy is (see also equation 4):

84 2 Thermodynamic Property Models


(1)
Where:
GE = Excess Gibbs energy
R = Gas constant
T = Temperature
nw = Kilograms of water
zi = Charge number of ion i
= molality of ion i

Where:
xi = Mole fraction of ion i
xw = Mole fraction of water
Mw = Molecular weight of water (g/mol)
ni = Moles of ion i

B, C, θ and Ψ are interaction parameters, and f(I) is an electrostatic term as


a function of ionic strength; these terms are discussed in Pitzer Activity
Coefficient Model, which has a detailed discussion of the Pitzer model.

The C term and the Ψ term are dropped from equation 1 to give the
simplified Pitzer equation.
(2)

Where:
Bij = f(βij(0),βij(1),βij(2),βij(3))
Therefore, the simplified Pitzer equation has two types of binary interaction
parameters, β 's and θ''s. There are no ternary interaction parameters with
the simplified Pitzer equation.
Note that the Pitzer model parameter databank described in Physical Property
Data, Chapter 1, is not applicable to the simplified Pitzer equation.

A built-in empirical correlation estimates the β(0) and β(1) parameters for
cation-anion pairs from the Bromley ionic parameters, βion and δion (Bromley,
1973). The estimated values of β(0)'s and β(1)'s are overridden by the user's

2 Thermodynamic Property Models 85


input. For parameter naming and requirements, see Bromley-Pitzer Activity
Coefficient Model.

References
L.A. Bromley, "Thermodynamic Properties of Strong Electrolytes in Aqueous
Solution, " AIChE J., Vol. 19, No. 2, (1973), pp. 313 – 320.
W. Fürst and H. Renon, "Effects of the Various Parameters in the Application
of Pitzer's Model to Solid-Liquid Equilibrium. Preliminary Study for Strong 1-1
Electrolytes," Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 3, (1982),
pp. 396-400.

Parameter Conversion
For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), the parameter
β(3) corresponds to Pitzer's β(1); β(2) is the same in both Aspen Physical
Property System and original Pitzer models. Pitzer refers to the n-m
electrolyte parameters as β(1), β(2), β(0). β(0) and β(2) retain their meanings in
both models, but Pitzer's β(1) is Aspen Physical Property System β(3). Be
careful to make this distinction when entering n-m electrolyte parameters.

Chien-Null
The Chien-Null model calculates liquid activity coefficients and it can be used
for highly non-ideal systems. The generalized expression used in its derivation
can be adapted to represent other well known formalisms for the activity
coefficient by properly defining its binary terms. This characteristic allows the
model the use of already available binary parameters regressed for those
other liquid activity models with thermodynamic consistency.
The equation for the Chien-Null liquid activity coeficient is:

Where:
Rji = Aji / Aij
Aii = 0

Aij = aij + bij / T


Subscripts i and j are component indices.
The choice of model and parameters can be set for each binary pair
constituting the process mixture by assigning the appropriate value to the
ICHNUL parameter.

86 2 Thermodynamic Property Models


The Regular Solution and Scatchard-Hamer models are regained by
substituting in the general expression (ICHNUL = 1 or 2).
Vji = Sji = Vj*,l / Vi*,l
Where:
Vj*,l = Liquid molar volume of component i
The Chien-Null activity coefficient model collapses to the Margules liquid
activity coefficient expression by setting (ICHNUL = 3):
Vji = Sji = 1
The Van Laar Liquid activity coefficient model is obtained when the V and S
parameters in the Chien-Null models are set to the ratio of the cross terms of
A (ICHNUL = 4:)
Vji = Sji = Aji / Aij
Finally, the Renon or NRTL model is obtained when we make the following
susbstitutions in the Chien-Null expression for the liquid activity (ICHNUL =
5).
Sji = RjiAji / Aij

Aji = 2τjiGji
Vji = Gji
The following are defined for the Non-Random Two-Liquid activity coefficient
model, where:

τij = aij + bij / T


Cij = cij + dij (T - 273.15 K)
cji = cij
dji = dij
The binary parameters CHNULL/1, CHNULL/2, and CHNULL/3 can be
determined from regression of VLE and/or LLE data. Also, if you have
parameters for many of the mixture pairs for the Margules, Van Laar,
Scatchard-Hildebrand, and NRTL (Non-Random-Two-Liquid) activity models,
you can use them directly with the Chien-Null activity model after selecting
the proper code (ICHNUL) to identify the source model and entering the
appropriate activity model parameters.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
ICHNUL — 3 1 6 —
CHNULL/1 aij 0 — — —
CHNULL/2 bij 0 — — —
CHNULL/3 Vij 0 — — —

The parameter ICHNUL is used to identify the activity model parameters


available for each binary pair of interest. The following values are allowed for
ICHNUL:

2 Thermodynamic Property Models 87


ICHNUL = 1 or 2, sets the model to the Scatchard-Hamer or regular solution
model for the associated binary;
ICHNUL = 3, sets the model to the Three-Suffix Margules activity model for
the associated binary;
ICHNUL = 4, sets the model to the Van Laar formalism for the activity model
for the associated binary;
ICHNUL = 5, sets the model to the NRTL (Renon) formalism for the activity
model for the associated binary.
ICHNUL = 6, sets the model to the full Chien-Null formalism for the activity
model for the associated binary.
When you specify a value for the ICHNUL parameter that is different than the
default, you must enter the appropriate binary model parameters for the
chosen activity model directly. The routine will automatically convert the
expressions and parameters to conform to the Chien-Null formulation.

Constant Activity Coefficient


This approach is used exclusively in metallurgical applications where multiple
liquid and solid phases can coexist. You can assign any value to the activity
coefficient of component i. Use the Properties Parameters Unary Scalar form.
The equation is:

γi = ai
Parameter Symbol Default MDS Upper Lower Units
Name/Element Limit Limit
GMCONS ai 1.0 x — — —

COSMO-SAC
Cosmo-SAC is a solvation model that describes the electric fields on the
molecular surface of species that are polarizable. It requires a fairly
complicated quantum mechanical calculation, but this calculation must be
done only once for a particular molecule; then the results can be stored. In its
final form, it uses individual atoms as the building blocks for predicting phase
equilibria instead of functional groups. This model formulation provides a
considerably larger range of applicability than group-contribution methods.
The calculation for liquid nonideality is only slightly more computationally
intensive than activity-coefficient models such as NRTL or UNIQUAC. Cosmo-
SAC complements the UNIFAC group-contribution method, because it is
applicable to virtually any mixture.
The Cosmo-SAC model calculates liquid activity coefficients. The equation for
the Cosmo-SAC model is:

With

88 2 Thermodynamic Property Models


Where:

γi = Activity coefficient of component i

γiSG = Staverman-Guggenheim model for combinatorial


contribution to γi

Γi(σm) = Segment activity coefficient of segment σm in


component i

2 Thermodynamic Property Models 89


ΓS(σm) = Segment activity coefficient of segment σm in
solvent mixture

pi(σm) = Sigma profile of component i

pi(σm) = Sigma profile of solvent mixture

σ = Surface charge density

ΔW(σm,σn) = Exchange energy between segments σm and σn


ΔWHB(σm,σn) = Hydrogen-bonding contribution to exchange energy
between segments σm and σn
z = Coordination number, 10
Vi = Molecular volume of component i
Ai = Molecular surface area of component i
aeff = Standard segment surface area, 7.50 Å2
Veff = Standard component volume, 66.69 Å3
Aeff = Standard component surface area, 79.53 Å2

α' = Misfit energy constant

The Cosmo-SAC model does not require binary parameters. For each
component, it has six input parameters. CSACVL is the component volume
parameter which is always defined in cubic angstroms, regardless of chosen
units sets. SGPRF1 to SGPRF5 are five component sigma profile parameters;
each can store up to 12 points of sigma profile values. All six input
parameters are obtained from COSMO calculation. The Aspen Physical
Property System includes a database of sigma profiles for over 1400
compounds from Mullins et al. (2006). The parameters were obtained by
permission from the Virginia Tech Sigma Profile Database website
(http://www.design.che.vt.edu/VT-2004.htm). Aspen Technology, Inc. does
not claim proprietary rights to these parameters.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CSACVL Vi — x — — VOLUME (Å3)
SGPRF1 Ai pi(1-12) — x — — —
SGPRF2 Ai pi(13-24) — x — — —
SGPRF3 Ai pi(25-36) — x — — —
SGPRF4 Ai pi(37-48) — x — — —
SGPRF5 Ai pi(49-51) — x — — —

Option Codes
The primary version of COSMO-SAC is the model by Lin and Sandler (2002).
Two other versions are available using an option code, as detailed in the table
below:

90 2 Thermodynamic Property Models


Option Description
Code
1 COSMO-SAC model by Lin and Sandler (2002)
2 COSMO-RS model by Klamt (1995)
3 Lin and Sandler model with modified exchange energy (Lin
et al., 2002)

References
A. Klamt, "Conductor-like Screening Model for Real Solvents: A New Approach
to the Quantitative Calculation of Solvation Phenomena," J. Phys. Chem. 99,
2224 (1995).
S.-T. Lin, P. M. Mathias, Y. Song, C.-C. Chen, and S. I. Sandler,
"Improvements of Phase-Equilibrium Predictions for Hydrogen-Bonding
Systems from a New Expression for COSMO Solvation Models," presented at
the AIChE Annual Meeting, Indianapolis, IN, 3-8 November (2002).
S.-T. Lin and S. I. Sandler, "A Priori Phase Equilibrium Prediction from a
Segment Contribution Solvation Model," Ind. Eng. Chem. Res. 41, 899
(2002).
E. Mullins, et al. "Sigma-Profile Database for Using COSMO-Based
Thermodynamic Methods," Ind. Eng. Chem. Res. 45, 4389 (2006).

Electrolyte NRTL Activity Coefficient Model


The Electrolyte Non-Random Two Liquid (NRTL) model is a versatile model for
the calculation of activity coefficients. Using binary and pair parameters, the
model can represent aqueous electrolyte systems as well as mixed solvent
electrolyte systems over the entire range of electrolyte concentrations. This
model can calculate activity coefficients for ionic species and molecular
species in aqueous electrolyte systems as well as in mixed solvent electrolyte
systems. The model reduces to the well-known NRTL model when electrolyte
concentrations become zero (Renon and Prausnitz, 1969).
The electrolyte NRTL model uses the infinite dilution aqueous solution as the
reference state for ions. It adopts the Born equation to account for the
transformation of the reference state of ions from the infinite dilution mixed
solvent solution to the infinite dilution aqueous solution.
Water must be present in the electrolyte system in order to compute the
transformation of the reference state of ions. Thus, it is necessary to
introduce a trace amount of water to use the model for nonaqueous
electrolyte systems.
The Aspen Physical Property System uses the electrolyte NRTL model to
calculate activity coefficients, enthalpies, and Gibbs energies for electrolyte
systems. Model development and working equations are provided in
Theoretical Basis and Working Equations.
The adjustable parameters for the electrolyte NRTL model include the:
• Pure component dielectric constant coefficient of nonaqueous solvents
• Born radius of ionic species

2 Thermodynamic Property Models 91


• NRTL parameters for molecule-molecule, molecule-electrolyte, and
electrolyte-electrolyte pairs
The pure component dielectric constant coefficients of nonaqueous solvents
and Born radius of ionic species are required only for mixed-solvent
electrolyte systems. The temperature dependency of the dielectric constant of
solvent B is:

Each type of electrolyte NRTL parameter consists of both the nonrandomness


factor, α, and energy parameters, τ. The temperature dependency relations
of the electrolyte NRTL parameters are:
• Molecule-Molecule Binary Parameters:

• Electrolyte-Molecule Pair Parameters:

• Electrolyte-Electrolyte Pair Parameters:


For the electrolyte-electrolyte pair parameters, the two electrolytes must
share either one common cation or one common anion:

Where:
Tref = 298.15K
Many parameter pairs are included in the electrolyte NRTL model parameter
databank (see Physical Property Data, Chapter 1).
Option codes can affect the performance of this model. See Option Codes for
Activity Coefficient Models for details.
Parameter Symbol No. of Default MDS Units
Name Elements
Dielectric Constant Unary Parameters
CPDIEC AB 1 — — —
BB 1 0 — —
CB 1 298.15 — TEMPERATURE†

92 2 Thermodynamic Property Models


Parameter Symbol No. of Default MDS Units
Name Elements
Ionic Born Radius Unary Parameters
RADIUS ri 1 3x10-10 — LENGTH
Molecule-Molecule Binary Parameters
NRTL/1 ABB' — 0 x —
AB'B — 0 x —
NRTL/2 BBB' — 0 x TEMPERATURE†
BB'B — 0 x TEMPERATURE†
NRTL/3 αBB' = αB'B — .3 x —

NRTL/4 — — 0 x TEMPERATURE
NRTL/5 FBB' — 0 x TEMPERATURE
FB'B — 0 x TEMPERATURE
NRTL/6 GBB' — 0 x TEMPERATURE
GB'B — 0 x TEMPERATURE
Electrolyte-Molecule Pair Parameters
GMELCC Cca,B 1 0 x —
CB,ca 1 0 x —
GMELCD Dca,B 1 0 x TEMPERATURE†
DB,ca 1 0 x TEMPERATURE†
GMELCE Eca,B 1 0 x —
EB,ca 1 0 x —
GMELCN αca,B = αB,ca 1 .2 x —
Electrolyte-Electrolyte Pair Parameters
GMELCC Cca',ca'' 1 0 x —
Cca'',ca' 1 0 x —
Cc'a,c''a 1 0 x —
Cc''a,c'a 1 0 x —

GMELCD Dca',ca'' 1 0 x TEMPERATURE

Dca'',ca' 1 0 x TEMPERATURE
Dc'a,c''a 1 0 x TEMPERATURE†
Dc''a,c'a 1 0 x TEMPERATURE†
GMELCE Eca',ca'' 1 0 x —
Eca'',ca' 1 0 x —
Ec'a,c''a 1 0 x —
Ec''a,c'a 1 0 x —
GMELCN αca',ca'' = αca'',ca' 1 .2 x —

αc'a,c''a = αc''a,c'a 1 .2 x —

Certain Electrolyte NRTL activity coefficient model parameters are used with
reciprocal temperature terms:
• CPDIEC
• NRTL/2
• GMELCD for electrolyte-electrolyte or electrolyte-molecule pairs

2 Thermodynamic Property Models 93


When any of these parameters is specified, absolute temperature units are
used for the calculations in this model.
Reference: H. Renon, and J.M. Prausnitz, "Local Compositions in
Thermodynamic Excess Functions for Liquid Mixtures", AIChE J., Vol. 14, No.
1, (1968), pp. 135-144.

Theoretical Basis and Working Equations


In this section, the theoretical basis of the model is explained and the working
equations are given. The different ways parameters can be obtained are
discussed with references to the databank directories and the Data
Regression System (DRS). The parameter requirements of the model are
given in Electrolyte NRTL Activity Coefficient Model.

Development of the Model


The Electrolyte NRTL model was originally proposed by Chen et al., for
aqueous electrolyte systems. It was later extended to mixed solvent
electrolyte systems (Mock et al., 1984, 1986). The model is based on two
fundamental assumptions:
• The like-ion repulsion assumption: states that the local composition of
cations around cations is zero (and likewise for anions around anions).
This is based on the assumption that the repulsive forces between ions of
like charge are extremely large. This assumption may be justified on the
basis that repulsive forces between ions of the same sign are very strong
for neighboring species. For example, in salt crystal lattices the immediate
neighbors of any central ion are always ions of opposite charge.
• The local electroneutrality assumption: states that the distribution of
cations and anions around a central molecular species is such that the net
local ionic charge is zero. Local electroneutrality has been observed for
interstitial molecules in salt crystals.
Chen proposed an excess Gibbs energy expression which contains two
contributions: one contribution for the long-range ion-ion interactions that
exist beyond the immediate neighborhood of a central ionic species, and the
other related to the local interactions that exist at the immediate
neighborhood of any central species.
The unsymmetric Pitzer-Debye-Hückel model and the Born equation are used
to represent the contribution of the long-range ion-ion interactions, and the
Non-Random Two Liquid (NRTL) theory is used to represent the local
interactions. The local interaction contribution model is developed as a
symmetric model, based on reference states of pure solvent and pure
completely dissociated liquid electrolyte. The model is then normalized by
infinite dilution activity coefficients in order to obtain an unsymmetric model.
This NRTL expression for the local interactions, the Pitzer-Debye-Hückel
expression, and the Born equation are added to give equation 1 for the
excess Gibbs energy (see the following note).

94 2 Thermodynamic Property Models


(1)

This leads to
(2)

Note: The notation using * to denote an unsymmetric reference state is well-


accepted in electrolyte thermodynamics and will be maintained here. The
reader should be warned not to confuse it with the meaning of * in classical
thermodynamics according to IUPAC/ISO, referring to a pure component
property. In fact in the context of G or γ, the asterisk as superscript is never
used to denote pure component property, so the risk of confusion is minimal.
For details on notation, see Chapter 1 of Physical Property Methods.

References
C.-C. Chen, H.I. Britt, J.F. Boston, and L.B. Evans, "Local Compositions Model
for Excess Gibbs Energy of Electrolyte Systems: Part I: Single Solvent, Single
Completely Dissociated Electrolyte Systems:, AIChE J., Vol. 28, No. 4, (1982),
p. 588-596.
C.-C. Chen, and L.B. Evans, "A Local Composition Model for the Excess Gibbs
Energy of Aqueous Electrolyte Systems," AIChE J., Vol. 32, No. 3, (1986), p.
444-459.
B. Mock, L.B. Evans, and C.-C. Chen, "Phase Equilibria in Multiple-Solvent
Electrolyte Systems: A New Thermodynamic Model," Proceedings of the 1984
Summer Computer Simulation Conference, p. 558.
B. Mock, L.B. Evans, and C.-C. Chen, "Thermodynamic Representation of
Phase Equilibria of Mixed-Solvent Electrolyte Systems," AIChE J., Vol. 32, No.
10, (1986), p. 1655-1664.

Long-Range Interaction Contribution


The Pitzer-Debye-Hückel formula, normalized to mole fractions of unity for
solvent and zero for electrolytes, is used to represent the long-range
interaction contribution.
(3)

with
(4)

(5)

Where:

2 Thermodynamic Property Models 95


xi = Mole fraction of component i
Ms = Molecular weight of the solvent

Aϕ = Debye-Hückel parameter

NA = Avogadro's number
ds = Mass density of solvent
Qe = Electron charge

εs = Dielectric constant of the solvent

T = Temperature
k = Boltzmann constant
Ix = Ionic strength (mole fraction scale)
xi = Mole fraction of component i
zi = Charge number of ion i

ρ = "Closest approach" parameter

Taking the appropriate derivative of equation 3, an expression for the activity


coefficient can then be derived.
(6)

The Born equation is used to account for the Gibbs energy of transfer of ionic
species from the infinite dilution state in a mixed-solvent to the infinite
dilution state in aqueous phase.
(7)

Where:

εw = Dielectric constant of water

ri = Born radius of the ionic species i


The expression for the activity coefficient can be derived from (7):
(8)

The Debye-Hückel theory is based on the infinite dilution reference state for
ionic species in the actual solvent media. For systems with water as the only
solvent, the reference state is the infinite dilution aqueous solution. For
mixed-solvent systems, the reference state for which the Debye-Hückel
theory remains valid is the infinite dilution solution with the corresponding
mixed-solvent composition. However, the molecular weight Ms, the mass
density ds, and the dielectric constant εs for the single solvent need to be

96 2 Thermodynamic Property Models


extended for mixed solvents; simple composition average mixing rules are
adequate to calculate them as follows:
(6a)

(7a)

(8a)

(8b)

(8c)

(8d)

Where:
xm = Mole fraction of the solvent m in the solution
Mm = Molecular weight of the solvent m
Vml = Molar volume of the solvent mixture

εm = Dielectric constant of the solvent m

Vw* = Molar volume of water using the steam table


xnws = Sum of the mole fractions of all non-water
solvents.
Vnwsl = Liquid molar volume for the mixture of all non-
water solvents. It is calculated using the
Rackett equation.
It should be understood that equations 6a-8a should be used only in
equations 3, 4, and 7. Ms, ds, and εs were already assumed as constants when
deriving equations 6 and 8 for mixed-solvent systems.

Local Interaction Contribution


The local interaction contribution is accounted for by the Non-Random Two
Liquid theory. The basic assumption of the NRTL model is that the nonideal
entropy of mixing is negligible compared to the heat of mixing: this is indeed
the case for electrolyte systems. This model was adopted because of its
algebraic simplicity and its applicability to mixtures that exhibit liquid phase
splitting. The model does not require specific volume or area data.

2 Thermodynamic Property Models 97


The effective local mole fractions Xji and Xii of species j and i, respectively, in
the neighborhood of i are related by:
(9)

Where:
Xj = xjCj
(Cj = zj for ions and Cj = unity for molecules)
Gji =

τji =

αji = Nonrandomness factor

gji and gii are energies of interaction between species j and i, and i and i,
respectively. Both gij and αij are inherently symmetric (gij = gji and αij = αji).
Similarly,
(10)

Where:
Gji,ki =

τji,ki =

αji,ki = Nonrandomness factor

Apparent Binary Systems


The derivations that follow are based on a simple system of one completely
dissociated liquid electrolyte ca and one solvent B. They will be later extended
to multicomponent systems. In this simple system, three different
arrangements exist:

98 2 Thermodynamic Property Models


In the case of a central solvent molecule with other solvent molecules,
cations, and anions in its immediate neighborhood, the principle of local
electroneutrality is followed: the surrounding cations and anions are such that
the neighborhood of the solvent is electrically neutral. In the case of a central
cation (anion) with solvent molecules and anions (cations) in its immediate
neighborhood, the principle of like-ion repulsion is followed: no ions of like
charge exist anywhere near each other, whereas opposite charged ions are
very close to each other.
The effective local mole fractions are related by the following expressions:
(11)
(central solvent cells)
(12)
(central cation cells)
(13)
(central anion cells)
Using equation 11 through 13 and the notation introduced in equations 9 and
10 above, expressions for the effective local mole fractions in terms of the
overall mole fractions can be derived.
(14)

i = c, a, or B
(15)

(16)

To obtain an expression for the excess Gibbs energy, let the residual Gibbs
energies, per mole of cells of central cation, anion, or solvent, respectively, be
, , and . These are then related to the
effective local mole fractions:
(17)

(18)

(19)

The reference Gibbs energy is determined for the reference states of


completely dissociated liquid electrolyte and of pure solvent. The reference
Gibbs energies per mole are then:
(20)

(21)

(22)

Where:

2 Thermodynamic Property Models 99


zc = Charge number on cations
za = Charge number on anions
The molar excess Gibbs energy can be found by summing all changes in
residual Gibbs energy per mole that result when the electrolyte and solvent in
their reference state are mixed to form the existing electrolyte system. The
expression is:
(23)

Using the previous relation for the excess Gibbs energy and the expressions
for the residual and reference Gibbs energy (equations 17 to 19 and 20 to
22), the following expression for the excess Gibbs energy is obtained:
(24)

The assumption of local electroneutrality applied to cells with central solvent


molecules may be stated as:
(25)

Combining this expression with the expression for the effective local mole
fractions given in equations 9 and 10, the following equality is obtained:
(26)

The following relationships are further assumed for nonrandomness factors:


(27)

(28)

and,
(29)

It can be inferred from equations 9, 10, and 26 to 29 that:


(30)

(31)

The binary parameters αca,B , τca,B and τB,ca are now the adjustable parameters
for an apparent binary system of a single electrolyte and a single solvent.
The excess Gibbs energy expression (equation 24) must now be normalized
to the infinite dilution reference state for ions:
(32)

This leads to:

100 2 Thermodynamic Property Models


(33)

By taking the appropriate derivatives of equation 33, expressions for the


activity coefficients of all three species can be determined.
(34)

(35)

(36)

Multicomponent Systems
The Electrolyte NRTL model can be extended to handle multicomponent
systems.
The excess Gibbs energy expression is:
(37)

Where:
j and k can be any species (a, C, or B)
The activity coefficient equation for molecular components is given by:

2 Thermodynamic Property Models 101


(38)

The activity coefficient equation for cations is given by:


(39)

The activity coefficient equation for anions is given by:


(40)

Where:
(41)

(42)

(43)

102 2 Thermodynamic Property Models


(44)

(45)

(46)

(47)

(48)

It should be understood that and remained constant in


equation 37 when deriving the activity coefficients given by equations 38-40.

Parameters
The model adjustable parameters include:
• Pure component dielectric constant coefficient of nonaqueous solvents
• Born radius of ionic species
• NRTL interaction parameters for molecule-molecule, molecule-electrolyte,
and electrolyte-electrolyte pairs
Note that for the electrolyte-electrolyte pair parameters, the two electrolytes
must share either one common cation or one common anion.
Each type of the electrolyte NRTL parameter consists of both the
nonrandomness factor, α, and energy parameters, τ.
The pure component dielectric constant coefficients of nonaqueous solvents
and Born radius of ionic species are required only for mixed-solvent
electrolyte systems.
The temperature dependency relations of these parameters are given in
Electrolyte NRTL Activity Coefficient Model.
Heat of mixing is calculated from temperature derivatives of activity
coefficients. Heat capacity is calculated from secondary temperature
derivative of the activity coefficient. As a result, the temperature dependent
parameters are critical for modeling enthalpy correctly. It is recommended
that enthalpy data and heat capacity data be used to obtain these
temperature dependency parameters. See also Electrolyte NRTL Enthalpy and
Electrolyte NRTL Gibbs Energy.

2 Thermodynamic Property Models 103


Obtaining Parameters
In the absence of electrolytes, the electrolyte NRTL model reduces to the
NRTL equation which is widely used for non-electrolyte systems. Therefore,
molecule-molecule binary parameters can be obtained from binary
nonelectrolyte systems.
Electrolyte-molecule pair parameters can be obtained from data regression of
apparent single electrolyte systems.
Electrolyte-electrolyte pair parameters are required only for mixed
electrolytes with a common ion. Electrolyte-electrolyte pair parameters can
affect trace ionic activity precipitation. Electrolyte-electrolyte pair parameters
can be obtained by regressing solubility data of multiple component
electrolyte systems.
When the electrolyte-molecule and electrolyte-electrolyte pair parameters are
zero, the electrolyte NRTL model reduces to the Debye-Hückel limiting law.
Calculation results with electrolyte-molecule and electrolyte-electrolyte pair
parameters fixed to zero should be adequate for very dilute weak electrolyte
systems; however, for concentrated systems, pair parameters are required
for accurate representation.
See Physical Property Data, Chapter 1, for the pair parameters available from
the electrolyte NRTL model databank. The table contains pair parameters for
some electrolytes in aqueous solution at 100°C. These values were obtained
by using the Aspen Physical Property Data Regression System (DRS) to
regress vapor pressure and mole fraction data at T=100°C with SYSOP15S
(Handbook of Chemistry and Physics, 56th Edition, CRC Press, 1975, p. E-1).
In running the DRS, standard deviations for the temperature (°C), vapor
pressure (mmHg), and mole fractions were set at 0.2, 1.0, and 0.001,
respectively. In addition, complete dissociation of the electrolyte was
assumed for all cases.

ENRTL-SAC
eNRTL-SAC (ENRTLSAC, patent pending) is an extension of the nonrandom
two-liquid segment activity coefficient model (NRTL-SAC, patent pending) by
Chen and Song (Ind. Eng. Chem. Res., 2004, 43, 8354) to include
electrolytes in the solution. It can be used in usable in Aspen Properties and
Aspen Polymers. It is intended for the computation of ionic activity
coefficients and solubilities of electrolytes, organic and inorganic, in common
solvents and solvent mixtures. In addition to the three types of molecular
parameters defined for organic nonelectrolytes in NRTL-SAC (hydrophobicity
X, hydrophilicity Z, and polarity Y- and Y+), an electrolyte parameter, E, is
introduced to characterize both local and long-range ion-ion and ion-molecule
interactions attributed to ionized segments of electrolytes.
In applying the segment contribution concept to electrolytes, a new
conceptual electrolyte segment e corresponding to the electrolyte parameter
E, is introduced. This conceptual segment e would completely dissociate to a
cationic segment (c) and an anionic segment (a), both of unity charge. All
electrolytes, organic or inorganic, symmetric or unsymmetric, univalent or
multivalent, are to be represented with this conceptual uni-univalent

104 2 Thermodynamic Property Models


electrolyte segment e together with previously defined hydrophobic segment
x, polar segments y- and y+, and hydrophilic segment z in NRTL-SAC.
A major consideration in the extension of NRTL-SAC for electrolytes is the
treatment of the reference state for activity coefficient calculations. While the
conventional reference state for nonelectrolyte systems is the pure liquid
component, the conventional reference state for electrolytes in solution is the
infinite-dilution aqueous solution and the corresponding activity coefficient is
unsymmetric. The equation for the logarithm of the unsymmetric activity
coefficient of an ionic species is

With

2 Thermodynamic Property Models 105


106 2 Thermodynamic Property Models
Where:
I, J = Component index
i, j, m, c, a = Conceptual segment index
m = Conceptual molecular segment, x, y-, y+, z
c = Conceptual cationic segment
a = Conceptual anionic segment
i, j = m,c,a

γI* = Unsymmetric activity coefficient of an ionic species I

γI*lc = NRTL term

γI*PDH = Pitzer-Debye-Hückel term

γI*FH = Flory-Huggins term

= Aqueous-phase infinite-dilution reference state

Γi = Activity coefficient of conceptual segment i

rI = Total segment number of component I


xI = Mole fraction of component I
rI,i = Number of conceptual segment i containing in component I
xi = Segment mole fraction of conceptual segment i in mixtures

αij = NRTL binary non-randomness factor parameter for


conceptual segments

τij = NRTL binary interaction energy parameter for conceptual


segments

Aϕ = Debye-Hückel parameter

ρ = Closest approach parameter, 14.9

Ix = Ionic strength (segment mole fraction scale)


= Average solvent molecular weight, g/mol

= Average solvent density, g/cm3

2 Thermodynamic Property Models 107


NA = Avogadro’s number
Qe = Absolute electronic charge
= Average solvent dielectric constant

εw = Water dielectric constant

rc = Born radius of cationic segment


ra = Born radius of anionic segment

NRTL binary parameters for conceptual segments


The NRTL binary parameters between conceptual molecular segments in are
determined by available VLE and LLE data between reference molecules
defined in NRTLSAC.
Segment (1) x x y- y+ x
Segment (2) y- z z z y+
τ12 1.643 6.547 -2.000 2.000 1.643

τ21 1.834 10.949 1.787 1.787 1.834

α12 = α21 0.2 0.2 0.3 0.3 0.2

NaCl is used as the reference electrolyte for the conceptual electrolyte


segment e. The NRTL binary parameters between conceptual molecular
segments and the electrolyte segment e are determined from literature data
or preset as follows:
Segment (1) x y- y+ z
Segment (2) e e e e
τ12 15 12 12 8.885

τ21 5 -3 -3 -4.549

α12 = α21 0.2 0.2 0.2 0.2

Parameters used in ENRTLSAC


Each component can have up to five parameters, rI,i (i = x, y-, y+, z, e),
although only one or two of these parameters are needed for most solvents
and ionic species in practice. Since conceptual segments apply to all species,
these five parameters are implemented together as a binary parameter,
NRTLXY(I, i) where I represents a component index and i represents a
conceptual segment index.

Option codes
There are three option codes in ENRTLSAC. The first is used to enable or
disable the Flory-Huggins term. The other two are only used internally and
you should not change their values. The Flory-Huggins term is included by
default in eNRTL-SAC model. You can remove this term using the first option
code. The table below lists the values for the first option code.
0 Flory-Huggins term included (default)

108 2 Thermodynamic Property Models


Others Flory-Huggins term removed

References
C.-C. Chen and Y. Song, "Solubility Modeling with a Nonrandom Two-Liquid
Segment Activity Coefficient Model," Ind. Eng. Chem. Res. 43, 8354 (2004).
C.-C. Chen and Y. Song, "Extension of Nonrandom Two-Liquid Segment
Activity Coefficient Model for Electrolytes," Ind. Eng. Chem. Res. 44, 8909
(2005).

Hansen
Hansen is a solubility parameter model and is commonly used in the solvent
selection process. It is based on the regular solution theory and Hansen
solubility parameters. This model has no binary parameters and its application
merely follows the empirical guide like dissolves like.
The Hansen model calculates liquid activity coefficients. The equation for the
Hansen model is:

with

Where:

γi = Activity coefficient of component i

Vi = Molar volume of component i

δid = Hansen solubility parameter of component i for nonpolar


effect

δip = Hansen solubility parameter of component i for polar effect

δih = Hansen solubility parameter of component i for hydrogen-


bonding effect

φi = Volume fraction of component i

2 Thermodynamic Property Models 109


xi = Mole fraction of component i
R = Gas constant
T = Temperature
The Hansen model does not require binary parameters. For each component,
it has four input parameters.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DELTAD δid — x — — PRESSURE^0.5

DELTAP δip — x — — PRESSURE^0.5

DELTAH δih — x — — PRESSURE^0.5

HANVOL Vi — x — — VOLUME

Option codes
The Hansen volume is implemented as an input parameter. If the Hansen
volume is not input by the user it will be calculated by an Aspen Plus internal
method. You can also request the Aspen Plus method using Option Codes in
Aspen Plus Interface. The table below lists the option codes.

First Option Code in Hansen model


0 Hansen volume input by user (default)
Other values Hansen volume calculated by Aspen Plus

Reference
Frank, T. C.; Downey, J. R.; Gupta, S. K. "Quickly Screen Solvents for
Organic Solids," Chemical Engineering Progress 1999, December, 41.
Hansen, C. M. Hansen Solubility Parameters: A User’s Handbook; CRC Press,
2000.

Ideal Liquid
This model is used in Raoult's law. It represents ideality of the liquid phase.
This model can be used for mixtures of hydrocarbons of similar carbon
number. It can be used as a reference to compare the results of other activity
coefficient models.
The equation is:

ln γi = 0

NRTL (Non-Random Two-Liquid)


The NRTL model calculates liquid activity coefficients for the following
property methods: NRTL, NRTL-2, NRTL-HOC, NRTL-NTH, and NRTL-RK. It is
recommended for highly non-ideal chemical systems, and can be used for VLE

110 2 Thermodynamic Property Models


and LLE applications. The model can also be used in the advanced equation-
of-state mixing rules, such as Wong-Sandler and MHV2.
The equation for the NRTL model is:

Where:
Gij =

τij =

αij =

τii = 0

Gii = 1
aij, bij, eij, and fij are unsymmetrical. That is, aij may not be equal to aji, etc.

Recommended cij Values for Different Types of Mixtures


cij Mixtures
0.30 Nonpolar substances; nonpolar with polar non-associated liquids; small
deviations from ideality
0.20 Saturated hydrocarbons with polar non-associated liquids and systems that
exhibit liquid-liquid immiscibility
0.47 Strongly self-associated substances with nonpolar substances

The binary parameters aij, bij, cij, dij, eij, and fij can be determined from VLE
and/or LLE data regression. The Aspen Physical Property System has a large
number of built-in binary parameters for the NRTL model. The binary
parameters have been regressed using VLE and LLE data from the Dortmund
Databank. The binary parameters for the VLE applications were regressed
using the ideal gas, Redlich-Kwong, and Hayden O'Connell equations of state.
See Physical Property Data, Chapter 1, for details.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
NRTL/1 aij 0 x -100.0 100.0 —
NRTL/2 bij 0 x -30000 30000.0 TEMPERATURE
NRTL/3 cij 0.30 x 0.0 1.0 —
NRTL/4 dij 0 x -0.02 0.02 TEMPERATURE
NRTL/5 eij 0 x — — TEMPERATURE
NRTL/6 fij 0 x — — TEMPERATURE

The NRTL-2 property method uses data set 2 for NRTL. All other NRTL
methods use data set 1.

2 Thermodynamic Property Models 111


References
H. Renon and J.M. Prausnitz, "Local Compositions in Thermodynamic Excess
Functions for Liquid Mixtures," AIChE J., Vol. 14, No. 1, (1968), pp. 135 –
144.

NRTL-SAC Model
NRTL-SAC (patent pending) is a segment contribution activity coefficient
model, derived from the Polymer NRTL model, but usable in Aspen Plus or
Aspen Properties without Aspen Polymers. NRTL-SAC can be used for fast,
qualitative estimation of the solubility of complex organic compounds in
common solvents. Conceptually, the model treats the liquid non-ideality of
mixtures containing complex organic molecules (solute) and small molecules
(solvent) in terms of interactions between three pairwise interacting
conceptual segments: hydrophobic segment (x), hydrophilic segment (z), and
polar segments (y- and y+). In practice, these conceptual segments become
the molecular descriptors used to represent the molecular surface
characteristics of each solute or solvent molecule. Hexane, water, and
acetonitrile are selected as the reference molecules for the hydrophobic,
hydrophilic, and polar segments, respectively. The molecular parameters for
all other solvents can be determined by regression of available VLE or LLE
data for binary systems of solvent and the reference molecules or their
substitutes. The treatment results in four component-specific molecular
parameters: hydrophobicity X, hydrophilicity Z, and polarity Y- and Y+. The
two types of polar segments, Y- and Y+, are used to reflect the wide
variations of interactions between polar molecules and water.
The conceptual segment contribution approach in NRTL-SAC represents a
practical alternative to the UNIFAC functional group contribution approach.
This approach is suitable for use in the industrial practice of carrying out
measurements for a few selected solvents and then using NRTL-SAC to
quickly predict other solvents or solvent mixtures and to generate a list of
suitable solvent systems.
The NRTL-SAC model calculates liquid activity coefficients.

Note: This is the updated version of NRTL-SAC, represented with property


model GMNRTLS and property method NRTL-SAC. This version does not
require the specification of components as oligomers. For the old version, see
NRTLSAC for Segments/Oligomers.
For the model equations, see NRTL-SAC Model Derivation.

Parameters used in NRTL-SAC


Each component can have up to four parameters, rx,I, ry-,I, ry+,I, and rz,I,
representing the equivalent number of segments of each type for the NRTL
activity coefficient model. Only one or two of these molecular parameters are
needed for most solvents in practice. These four molecular parameters are
implemented together as pure parameter XYZE with four elements
representing these four parameters. Values for this parameter are available
for many common solvents in the NRTL-SAC databank.

112 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Limit Units
Name/ Limit
Element
XYZE/1 rx,I — — — — —
XYZE/2 ry-,I — — — — —
XYZE/3 ry+,I — — — — —
XYZE/4 rz,I — — — — —
XYZE/5 not used — — — — —

NRTL-SAC Model Derivation


NRTL-SAC activity coefficient model for component I is composed of the
combinatorial term, ln γIC, and the residual term, ln γIR:
(1)

Here the combinatorial term, γIC, is calculated from the Flory-Huggins


equation for the combinatorial entropy of mixing. The residual term, γIR, is
calculated from the local composition (lc) interaction contribution, γIlc, of
Polymer NRTL (Chen, 1993). The Polymer NRTL equation incorporates the
segment interaction concept and it computes activity coefficient for
component I in a solution by summing up contributions to activity coefficient
from all segments that makes up component I.
Flory-Huggins Term
The excess Gibbs free energy from the Flory-Huggins model is given as
follows:
(2)

with
(3)

where I and J denote component index; nI and xJ are the mole number and
mole fraction of component I, respectively; φI is the segment fraction of
component I; and rI is the total number of segments in component I:
(4)

where i denotes the segment-based species index and ri,I is the number of
segment species i in component I.
The activity coefficient of component I from the entropy of mixing can be
calculated as follows:

2 Thermodynamic Property Models 113


(5)

Local Interaction Contributions


The excess Gibbs free energy from local interactions can be written as
follows:
(6)

(7)

(8)

(9)

where G and τ are local binary quantities related to each other by the NRTL
non-random factor parameter α:
(10)

To compute the local composition term for the activity coefficients of


components, we first compute local composition contributions for each
segment. For this purpose, we rewrite Eq. 6 as follows:
(11)

or
(12)

Accordingly, the segment activity coefficient can be calculated as follows:

114 2 Thermodynamic Property Models


(13)

The local composition term for the logarithm of activity coefficient of


component I is then computed as the sum of the individual segment
contributions.
(14)

However, the activity coefficient by Eq. 14 needs to be further normalized so


that γIlc = 1 as xI→1 for any component; the normalization can be done as
follows:
(15)

whereγIlc,I is the activity coefficient of the segment species i contained in the


pure component I; it can be calculated as follows:
(16)

(17)

Henry Components
The infinite-dilution activity coefficient in mixed-solvent solutions for Henry
component H is given as follows:
(18)

(19)

(20)

2 Thermodynamic Property Models 115


(21)

(22)

(23)

Notice that xH→0 applies to all Henry components in the solution.


The infinite-dilution activity coefficient of Henry component H in a solvent S
(i.e., xH→0 and xS→1) is given as follows:
(24)

(25)

(26)

NRTLSAC for Segments/Oligomers


This is the original NRTLSAC model added in version 2006, which requires
that components be defined as oligomers. It is retained for compatibility, but
new models should use the NRTL-SAC model.
NRTL-SAC (patent pending) is a segment contribution activity coefficient
model, derived from the Polymer NRTL model, usable in Aspen Properties and
Aspen Polymers. NRTL-SAC can be used for fast, qualitative estimation of the
solubility of complex organic compounds in common solvents. Conceptually,
the model treats the liquid non-ideality of mixtures containing complex
organic molecules (solute) and small molecules (solvent) in terms of
interactions between three pairwise interacting conceptual segments:
hydrophobic segment (x), hydrophilic segment (z), and polar segments (y-
and y+). In practice, these conceptual segments become the molecular
descriptors used to represent the molecular surface characteristics of each
solute or solvent molecule. Hexane, water, and acetonitrile are selected as

116 2 Thermodynamic Property Models


the reference molecules for the hydrophobic, hydrophilic, and polar segments,
respectively. The molecular parameters for all other solvents can be
determined by regression of available VLE or LLE data for binary systems of
solvent and the reference molecules or their substitutes. The treatment
results in four component-specific molecular parameters: hydrophobicity X,
hydrophilicity Z, and polarity Y- and Y+. The two types of polar segments, Y-
and Y+, are used to reflect the wide variations of interactions between polar
molecules and water.
The conceptual segment contribution approach in NRTL-SAC represents a
practical alternative to the UNIFAC functional group contribution approach.
This approach is suitable for use in the industrial practice of carrying out
measurements for a few selected solvents and then using NRTL-SAC to
quickly predict other solvents or solvent mixtures and to generate a list of
suitable solvent systems.
The NRTL-SAC model calculates liquid activity coefficients.
The equation for the NRTL-SAC model is:

with

2 Thermodynamic Property Models 117


G = exp(-ατ)
Where:
I, J = Component index
i, j, m = Conceptual segment indexx, y-, y+, z

γI = Activity coefficient of component I

γIC = γIFH = Flory-Huggins term for combinatorial contribution to γI


γIR = γIlc = NRTL term for local composition interaction contribution to
γI
φI = Segment mole fraction of component I

pI = Effective component size parameter

sI and εI = Empirical parameters for pI

rI = Total segment number of component I


xI = Mole fraction of component I
rI,m = Number of conceptual segment m containing in component
I
xi = Segment mole fraction of conceptual segment i in mixtures

αim = NRTL binary non-randomness factor parameter for


conceptual segments

τim = NRTL binary interaction energy parameter for conceptual


segments

NRTL binary parameters for conceptual segments


The NRTL binary parameters between conceptual segments in NRTLSAC are
determined by available VLE and LLE data between reference molecules
defined above.
Segment 1 x x y- y+ x
Segment 2 y- z z z y+
τ12 1.643 6.547 -2.000 2.000 1.643

τ21 1.834 10.949 1.787 1.787 1.834

α12 = α21 0.2 0.2 0.3 0.3 0.2

Parameters used in NRTLSAC


Each component can have up to four parameters, rI,x, rI,y-, rI,y+, and rI,z
although only one or two of these molecular parameters are needed for most
solvents in practice. Since conceptual segments apply to all molecules, these
four molecular parameters are implemented together as a binary parameter,

118 2 Thermodynamic Property Models


NRTLXY(I, m) where I represents a component (molecule) index and m
represents a conceptual segment index.
In addition, the Flory-Huggins size parameter, FHSIZE , is used in NRTLSAC
to calculate the effective component size parameter, pI. The Flory-Huggins
combinatorial term can be turned off by setting εI = 0 for each component in
mixtures.
Parameter Symbol Default MDS Lower Upper Units Comment
Name/ Limit Limit
Element
NRTLXY rI,m — — — — — Binary,
symmetric
FHSIZE/1 sI 1.0 — 1E-15 1E15 — Unary
FHSIZE/2 εI 1.0 — -1E10 1E10 — Unary

Option codes
The Flory-Huggins term is included by default in the NRTLSAC model. You can
remove this term using the first option code. The table below lists the values
for this option code.
0 Flory-Huggins term included (default)
Others Flory-Huggins term removed

NRTLSAC molecular parameters for common solvents


The molecular parameters are identified for 62 solvents and published.
Solvent name rI,x rI,y- rI,y+ rI,z
ACETIC-ACID 0.045 0.164 0.157 0.217
ACETONE 0.131 0.109 0.513
ACETONITRILE 0.018 0.131 0.883
ANISOLE 0.722
BENZENE 0.607 0.190
1-BUTANOL 0.414 0.007 0.485
2-BUTANOL 0.335 0.082 0.355
N-BUTYL-ACETATE 0.317 0.030 0.330
METHYL-TERT-BUTYL-ETHER 1.040 0.219 0.172
CARBON-TETRACHLORIDE 0.718 0.141
CHLOROBENZENE 0.710 0.424
CHLOROFORM 0.278 0.039
CUMENE 1.208 0.541
CYCLOHEXANE 0.892
1,2-DICHLOROETHANE 0.394 0.691
1,1-DICHLOROETHYLENE 0.529 0.208
1,2-DICHLOROETHYLENE 0.188 0.832
DICHLOROMETHANE 0.321 1.262

2 Thermodynamic Property Models 119


Solvent name rI,x rI,y- rI,y+ rI,z
1,2-DIMETHOXYETHANE 0.081 0.194 0.858
N,N-DIMETHYLACETAMIDE 0.067 0.030 0.157
N,N-DIMETHYLFORMAMIDE 0.073 0.564 0.372
DIMETHYL-SULFOXIDE 0.532 2.890
1,4-DIOXANE 0.154 0.086 0.401
ETHANOL 0.256 0.081 0.507
2-ETHOXYETHANOL 0.071 0.318 0.237
ETHYL-ACETATE 0.322 0.049 0.421
ETHYLENE-GLYCOL 0.141 0.338
DIETHYL-ETHER 0.448 0.041 0.165
ETHYL-FORMATE 0.257 0.280
FORMAMIDE 0.089 0.341 0.252
FORMIC-ACID 0.707 2.470
N-HEPTANE 1.340
N-HEXANE 1.000
ISOBUTYL-ACETATE 1.660 0.108
ISOPROPYL-ACETATE 0.552 0.154 0.498
METHANOL 0.088 0.149 0.027 0.562
2-METHOXYETHANOL 0.052 0.043 0.251 0.560
METHYL-ACETATE 0.236 0.337
3-METHYL-1-BUTANOL 0.419 0.538 0.314
METHYL-BUTYL-KETONE 0.673 0.224 0.469
METHYLCYCLOHEXANE 1.162 0.251
METHYL-ETHYL-KETONE 0.247 0.036 0.480
METHYL-ISOBUTYL-KETONE 0.673 0.224 0.469
ISOBUTANOL 0.566 0.067 0.485
N-METHYL-2-PYRROLIDONE 0.197 0.322 0.305
NITROMETHANE 0.025 1.216
N-PENTANE 0.898
1-PENTANOL 0.474 0.223 0.426 0.248
1-PROPANOL 0.375 0.030 0.511
ISOPROPYL-ALCOHOL 0.351 0.070 0.003 0.353
N-PROPYL-ACETATE 0.514 0.134 0.587
PYRIDINE 0.205 0.135 0.174
SULFOLANE 0.210 0.457
TETRAHYDROFURAN 0.235 0.040 0.320
1,2,3,4-TETRAHYDRONAPHTHALENE 0.443 0.555
TOLUENE 0.604 0.304
1,1,1-TRICHLOROETHANE 0.548 0.287

120 2 Thermodynamic Property Models


Solvent name rI,x rI,y- rI,y+ rI,z
TRICHLOROETHYLENE 0.426 0.285
M-XYLENE 0.758 0.021 0.316
WATER 1.000
TRIETHYLAMINE 0.557 0.105
1-OCTANOL 0.766 0.032 0.624 0.335

Reference
C.-C. Chen and Y. Song, "Solubility Modeling with a Nonrandom Two-Liquid
Segment Activity Coefficient Model," Ind. Eng. Chem. Res. 43, 8354 (2004).

Using NRTLSAC
NRTLSAC (patent pending) is a segment contribution activity coefficient
model, derived from the Polymer NRTL model, usable in Aspen Properties and
Aspen Polymers. NRTLSAC can be used for fast, qualitative estimation of the
solubility of complex organic compounds in common solvents. For more
information about the model, see NRTLSAC for Segments/Oligomers.

Note: A newer version of NRTL-SAC comes with its own property method
named NRTL-SAC and does not require the specification of a method and
oligomer components as described below.
The NRTLSAC model for Segments/Oligomers in the Aspen Physical Property
System is a liquid activity coefficient model called NRTLSAC. To specify it:
1. On the Properties | Specifications sheet, specify process type ALL.
2. Specify base method NRTLSAC.
In order to use this version of NRTLSAC, all components must be defined as
oligomers. Four conceptual segments also must be defined. On the
Components | Polymers | Oligomers sheet, enter a number for at least
one conceptual segment for each oligomer component, as required by the
definition of an oligomer. These numbers are not used by NRTL-SAC.
On the Properties | Parameters | Binary Interaction | NRTL-1 form,
enter the binary parameters between conceptual segments. In the following
example, the conceptual segments are named X, Y-, Y+, and Z.
Segment 1 X X Y- Y+ X
Segment 2 Y- Z Z Z Y+
AIJ 1.643 6.547 -2.000 2.000 1.643
AJI 1.834 10.949 1.787 1.787 1.834
CIJ 0.2 0.2 0.3 0.3 0.2

On the Properties | Parameters | Binary Interaction | NRTLXY-1 form,


enter a non-zero value for at least one of the four parameters for each
component.

2 Thermodynamic Property Models 121


Pitzer Activity Coefficient Model
The Pitzer model was developed as an improvement upon an earlier model
proposed by Guggenheim (1935, 1955). The earlier model worked well at low
electrolyte concentrations, but contained discrepancies at higher
concentrations (>0.1M). The Pitzer model resolved these discrepancies,
without resorting to excessive arrays of higher-order terms.
The model can be used for aqueous electrolyte systems, up to 6 molal ionic
strength. It cannot be used for systems with any other solvent or mixed
solvents.
This section provides theoretical background for the model. All model
equations and parameter requirements are included.
The Pitzer model is commonly used in the calculation of activity coefficients
for aqueous electrolytes up to 6 molal ionic strength. Do not use this model if
a non-aqueous solvent exists. Henry's law parameters are required for all
other components in the aqueous solution. The model development and
working equations are provided in the following sections. Parameter
conversion between the Pitzer notation and our notation is also provided.
The Pitzer model in the Aspen Physical Property System involves user-
supplied parameters that are used in the calculation of binary and ternary
parameters for the electrolyte system.
Five elements (P1 through P5) account for the temperature dependencies of
ϕ
parameters β(0), β(1), β(2), β(3), C , θ, and Ψ. These parameters follow the
temperature dependency relation:

Where:
Tref = 298.15 K
The user must:
• Supply these elements for the binary parameters using a Properties |
Parameters | Binary | T-Dependent form.
• Supply these elements for Ψ on the Properties | Parameters | Electrolyte
Ternary form.
• Specify Comp ID i and Comp ID j (and Comp ID k for Ψ) on these forms,
using the same order that appears on the Components Specifications
Selection sheet.
The parameters are summarized in the following table. There is a Pitzer
parameter databank in the Aspen Physical Property System (see Physical
Property Data).
Parameter Provides No. of Default MDS Units
Name P1 - P5 for Elements
Cation-Anion Parameters
GMPTB0 β(0) 5 0 x —

GMPTB1 β(1) 5 0 x —

122 2 Thermodynamic Property Models


Parameter Provides No. of Default MDS Units
Name P1 - P5 for Elements
GMPTB2 β(2) 5 0 x —

GMPTB3 β(3) 5 0 x —

GMPTC ϕ 5 0 x —
C
Cation-Cation Parameters
GMPTTH θcc' 5 0 x —

Anion-Anion Parameters
GMPTTH θaa' 5 0 x —

Ternary Parameters
GMPTPS, Ψijk 1 (in each 0 x —
GMPTP1, parameter)
GMPTP2,
GMPTP3,
GMPTP4
Molecule-Ion and Molecule-Molecule Parameters
GMPTB0 β(0) 5 0 x —

GMPTB1 β(1) 5 0 x —

GMPTC ϕ 5 0 x —
C

Model Development
The Pitzer model analyzes "hard-core" effects in the Debye-Hückel theory. It
uses the following expansion as a radial distribution function:
(1)

Where:
gij = Distribution function
r = Radius
qij =

(pair potential of mean force)


With:
zi = Charge of ion i
Qe = Electron charge

Ψj(r) = Average electric potential for ion j

k = Boltzmann's constant
T = Temperature
This radial distribution function is used in the so-called pressure equation that
relates this function and the intermolecular potential to thermodynamic

2 Thermodynamic Property Models 123


properties. From this relation you can obtain an expression for the osmotic
coefficient.
Pitzer proposes a general equation for the excess Gibbs energy. The basic
equation is:
(2)

Where:
GE = Excess Gibbs energy
R = Gas constant
T = Temperature
nw = Kilograms of water
mi =

(molality of ion i)
With:
xi = Mole fraction of ion i
xw = Mole fraction of water
Mw = Molecular weight of water (g/mol)
ni = Moles of ion i
The function f(I) is an electrostatic term that expresses the effect of long-
range electrostatic forces between ions. This takes into account the hard-core
effects of the Debye-Hückel theory. This term is discussed in detail in the
following section. The parameters λij are second virial coefficients that
account for the short-range forces between solutes i and j. The parameters
μijk account for the interactions between solutes, i, j, k. For ion-ion
interactions, λij is a function of ionic strength. For molecule-ion or molecule-
molecule interactions this ionic strength dependency is neglected. The
dependence of μijk on ionic strength is always neglected. The matrices λij and
μijk are also taken to be symmetric (that is, λij = λji).
Pitzer modified this expression for the Gibbs energy by identifying
combinations of functions. He developed interaction parameters that can be
evaluated using experimental data. He selected mathematical expressions for
these parameters that best fit experimental data.
Pitzer's model can be applied to aqueous systems of strong electrolytes and
to aqueous systems of weak electrolytes with molecular solutes. These
applications are discussed in the following section.
In the Aspen Physical Property System, this model is applied using the
reference state of infinite dilution solution in water for non-water molecular
solutes and ionic species. The properties such as DHAQFM are obtained at 25
C and 1 atm.

124 2 Thermodynamic Property Models


Application of the Pitzer Model to Aqueous Strong
Electrolyte Systems
Pitzer modified his basic equation to make it more useful for data correlation
of aqueous strong electrolytes. He defined a set of more directly observable
parameters to represent combinations of the second and third virial
coefficients. The modified Pitzer equation is:
(3)

zi = Charge of ion i

Subscripts c, c', and a, a' denote cations and anions of the solution. B, C, θ,
and Ψ are interaction parameters. f(I) is an electrostatic term as a function of
ionic strength. The cation-anion parameters B and C are characteristic for an
aqueous single-electrolyte system. These parameters can be determined by
the properties of pure (apparent) electrolytes. B is expressed as a function of
β(0) and β(1), or of β(0), β(2), and β(3) (see equations 11 through 15).
The parameters θ and Ψ are for the difference of interaction of unlike ions of
the same sign from the mean of like ions. These parameters can be measured
from common-ion mixtures. Examples are NaCl + KCl + H2O or NaCl + NaNO3
+ H2O (sic, Pitzer, 1989). These terms are discussed in detail later in this
section.
Fürst and Renon (1982) propose the following expression as the Pitzer
equation for the excess Gibbs energy:
(4)

The difference between equations 3 and 4 is that Pitzer orders cation before
anions. Fürst and Renon do not. All summations are taken over all ions i and j
(both cations and anions). This involves making the parameter matrices Bij,
Cij, θij, and Ψijk symmetric, as follows:
Second-order parameters are written Bij if i and j are ions of different sign. Bij
= 0 if the sign of zi = sign of zj, and Bii = 0. Since cations are not ordered
before anions, Bij = Bji. This eliminates the 2 in the second term in brackets in
Pitzer's original expression (equation 3). Second-order parameters are written
θij if i and j are ions of the same sign. Thus θij = 0 if the sign of zi is different
from the sign of zj, and θii = 0 with θij = θji.

2 Thermodynamic Property Models 125


Third-order parameters are written Cij if i and j are ions with different signs.
Cij = 0 if the sign of zi = sign of zj, and Cii = 0 with Cij = Cji. The factor of 2 in
the fifth bracketed term in Pitzer's original expression (equation 3) becomes

1/2 in equation 4. The matrix C is symmetric and is extended to all


ions to make the equation symmetric.

Ψijk is written for three different ions Ψijk = Ψkij = Ψjki , and Ψikk = 0. Ψijk = 0
if the sign of zi =sign of zj =sign of zk. The factor of 1/6 is different from 1/2
in the last term in brackets in Pitzer's original expression. Pitzer distinguishes
between cations and anions. In Pitzer's original model this parameter appears
twice, as Ψcc'a and Ψc'ca. In this modified model, it appears six times, as Ψcc'a;
Ψc'ca; Ψacc'; Ψac'c; Ψcac'; and Ψc'ac. Fürst and Renon's expression, equation 4,
calculates the expressions for activity coefficients and osmotic coefficients.
Pitzer (1975) modified his model by adding the electrostatic unsymmetrical
mixing effects, producing this modified Pitzer equation for the excess Gibbs
energy:
(4a)

Calculation of Activity Coefficients


The natural logarithm of the activity coefficient for ions is calculated from
equation 4a to give:
(5)

Where θ is neglected and Φij and Φ'ij are the electrostatic unsymmetric mixing
effects:

126 2 Thermodynamic Property Models


The X parameters are calculated differently on the option code.
For option code = –1, there is no unsymmetric mixing correction term:

For option code = 0 (default), the unsymmetric mixing correction term is in


polynomial form:

For option code = 1, the unsymmetric mixing correction term is in integral


form:

For water the logarithm of the activity coefficient is calculated similarly, as


follows:
Applying:

to equation 3 and using:

Where Nw = moles water, gives:

2 Thermodynamic Property Models 127


(6)

f(I), the electrostatic term, is expressed as a function of ionic strength I :


(7)

I, the ionic strength, is defined as:


(8)

Taking the derivative of equation 7 with respect to I, gives:


(9)

So that:
(10)

This equation is used in equation 6. In equations 7 and 9, is the usual Debye-


Hückel constant for the osmotic coefficient, determined from:
(11)

Where:
NA = Avogadro's constant
dw = Water density

εB = Dielectric constant of solvent B

b is an adjustable parameter, which has been optimized in this model to equal


1.2.
B and B' need expressions so that equations 5 and 6 can completely be solved
for the activity coefficients. The parameter B is determined differently for
different electrolyte pairings. For 1-n electrolytes (1-1, 1-2, 2-1, and so on)
the following expression gives the parameter B:
(12)

with α1=2.0.
For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), B is determined
by the following expression:

128 2 Thermodynamic Property Models


(13)

with α2 = 12.0 and α3 = 1.4.


By taking appropriate derivatives, expressions for B' can be derived for 1–n
electrolytes:
(14)

and for n-m electrolytes:


(15)

The parameters β(0), β(1), β(2), β(3) and also C, θ, and Ψ can be found in
Pitzer's articles .
After the activity coefficients are calculated, they can be converted to the
mole fraction scale from the molality scale by the following relations:
For solutes:
(16)

For water as a solvent:


(17)

Where:

γm = Activity coefficient (molality scale)

γx = Activity coefficient (mole fraction scale)

2 Thermodynamic Property Models 129


Application of the Pitzer Model to Aqueous
Electrolyte Systems with Molecular Solutes
In aqueous weak electrolyte systems with molecular solutes, the second and
third virial coefficients in the basic Pitzer equation for molecule-ion and
molecule-molecule interactions must be considered. The following extensions
of Pitzer's interaction parameters are made.
The second-order parameters Bij are extended to include molecule-molecule
and molecule-ion interaction parameters.

The third-order parameters Ψijk are extended to molecule-molecule-molecule


interactions. The following expressions relate Ψijk to Pitzer's original μijk:

Ψiii = 6μiii
However, molecule-molecule interactions were not taken into account by
Pitzer and coworkers. So μiii is an artificially introduced quantity.
The equations for activity coefficients and the Gibbs free energy are the same
as equations 3 through 6.

Parameters
The Pitzer model in the Aspen Physical Property System involves user-
supplied parameters. These parameters are used in the calculation of binary
and ternary parameters for the electrolyte system. These parameters include
ϕ
the cation-anion parameters β(0), β(1), β(2), β(3) and C , cation-cation
parameter θcc', anion-anion parameter θaa', cation1-cation2-common anion
parameter Ψcc'a, anion1-anion2-common cation parameter Ψcaa', and the
ϕ
molecule-ion and molecule-molecule parameters β(0), β(1), and, C . The
parameter names in the Aspen Physical Property System and their
requirements are discussed in Pitzer Activity Coefficient Model.

Parameter Conversion
For n-m electrolytes, n and m>1 (2-2, 2-3, 3-4, and so on), the parameter
β(3) corresponds to Pitzer's β(1). β(2) is the same in both the Aspen Physical
Property System and original Pitzer models. Pitzer refers to the n-m
electrolyte parameters as β(1), β(2), β(0). β(0) and β(2) retain their meanings in
both models, but Pitzer's β(1) is β(3) in the Aspen Physical Property System. Be
careful to make this distinction when entering n-m electrolyte parameters.
ϕ
Pitzer often gives values of β(0), β(1), β(2), β(3), and C that are corrected by
some factors (see Pitzer and Mayorga (1973) for examples). These factors
originate from one of Pitzer's earlier expressions for the excess Gibbs energy:
(18)

130 2 Thermodynamic Property Models


Where:
=

na = Mole number of anions


nc = Mole number of cation

Here β(0), β(1), β(2), and β(3) are multiplied by a factor of 2ncna. C is multiplied
by a factor of 2(ncna)3/2.
Aspen Physical Property System accounts for these correcting factors. Enter
the parameters without their correcting factors.
For example, Pitzer gives the values of parameters for MgCl2 as:

4/3β(0) = 0.4698

4/3β(1) = 2.242

= 0.00979

Perform the necessary conversions and enter the parameters as:


= 0.3524

= 1.6815

= 0.00520

Parameter Sources
Binary and ternary parameters for the Pitzer model for various electrolyte
systems are available from Pitzer's series on the thermodynamics of
electrolytes. These papers and the electrolyte parameters they give are:
Reference Parameters available
ϕ
(Pitzer, 1973) Binary parameters (β(0), β(1), C ) for 13
dilute aqueous electrolytes
(Pitzer and Mayorga, 1973) Binary parameters for 1-1 inorganic
electrolytes, salts of carboxylic acids (1-1),
tetraalkylammonium halids, sulfonic acids
and salts, additional 1-1 organic salts, 2-1
inorganic compounds, 2-1 organic
electrolytes, 3-1 electrolytes, 4-1 and 5-1
electrolytes
(Pitzer and Mayorga, 1974) Binary parameters for 2-2 electrolytes in
water at 25°C
(Pitzer and Kim, 1974) Binary and ternary parameters for mixed
electrolytes, binary mixtures without a
common ion, mixed electrolytes with three
or more solutes

2 Thermodynamic Property Models 131


Reference Parameters available
(Pitzer, 1975) Ternary parameters for systems mixing
doubly and singly charged ions
(Pitzer and Silvester, 1976) Parameters for phosphoric acid and its buffer
solutions
(Pitzer, Roy and Silvester, 1977) Parameters and thermodynamic properties
for sulfuric acid
(Silvester and Pitzer, 1977) Data for NaCl and aqueous NaCl solutions
(Pitzer, Silvester, and Peterson, 1978) Rare earth chlorides, nitrates, and
perchlorates
(Peiper and Pitzer, 1982) Aqueous carbonate solutions, including
mixtures of sodium carbonate, bicarbonate,
and chloride
(Phutela and Pitzer, 1983) Aqueous calcium chloride
(Conceicao, de Lima, and Pitzer, 1983) Saturated aqueous solutions, including
mixtures of sodium chloride, potassium
chloride, and cesium chloride
(Pabalan and Pitzer, 1987) Parameters for polynomial unsymmetric
mixing term
(Kim and Frederick, 1988) Parameters for integral unsymmetric mixing
term

Pitzer References
Conceicao, M., P. de Lima, and K.S. Pitzer, "Thermodynamics of Saturated
Aqueous Solutions Including Mixtures of NaCl, KCl, and CsCl, "J. Solution
Chem, Vol. 12, No. 3, (1983), pp. 171-185.
Fürst, W. and H. Renon, "Effects of the Various Parameters in the Application
of Pitzer's Model to Solid-Liquid Equilibrium. Preliminary Study for Strong 1-1
Electrolytes," Ind. Eng. Chem. Process Des. Dev., Vol. 21, No. 3, (1982),
pp. 396-400.
Guggenheim, E.A., Phil. Mag., Vol. 7, No. 19, (1935), p. 588.
Guggenheim, E.A. and J.C. Turgeon, Trans. Faraday Soc., Vol. 51, (1955), p.
747.
Kim, H. and W.J. Frederick, "Evaluation of Pitzer Ion Interaction Parameters
of Aqueous Mixed Electrolyte Solution at 25C, Part 2: Ternary Mixing
Parameters," J. Chem. Eng. Data, 33, (1988), pp. 278-283.
Pabalan, R.T. and K.S. Pitzer, "Thermodynamics of Concentrated Electrolyte
Mixtures and the Prediction of Mineral Solubilities to High Temperatures for
Mixtures in the system Na-K-Mg-Cl-SO4-OH-H2O," Geochimica Acta, 51,
(1987), pp. 2429-2443.
Peiper, J.C. and K.S. Pitzer, "Thermodynamics of Aqueous Carbonate
Solutions Including Mixtures of Sodium Carbonate, Bicarbonate, and
Chloride," J. Chem. Thermodynamics, Vol. 14, (1982), pp. 613-638.
Phutela, R.C. and K.S. Pitzer, "Thermodynamics of Aqueous Calcium
Chloride," J. Solution Chem., Vol. 12, No. 3, (1983), pp. 201-207.

132 2 Thermodynamic Property Models


Pitzer, K.S., "Thermodynamics of Electrolytes. I. Theoretical Basis and
General Equations, " J. Phys. Chem., Vol. 77, No. 2, (1973), pp. 268-277.
Pitzer, K.S., J. Solution Chem., Vol. 4, (1975), p. 249.
Pitzer, K.S., "Fluids, Both Ionic and Non-Ionic, over Wide Ranges of
Temperature and Composition," J. Chen. Thermodynamics, Vol. 21, (1989),
pp. 1-17. (Seventh Rossini lecture of the commission on Thermodynamics of
the IUPAC, Aug. 29, 1988, Prague, ex-Czechoslovakia).
Pitzer, K.S. and J.J. Kim, "Thermodynamics of Electrolytes IV; Activity and
Osmotic Coefficients for Mixed Electrolytes," J.Am. Chem. Soc., Vol. 96
(1974), p. 5701.
Pitzer, K.S. and G. Mayorga, "Thermodynamics of Electrolytes II; Activity and
Osmotic Coefficients for Strong Electrolytes with One or Both Ions Univalent,"
J. Phys. Chem., Vol. 77, No. 19, (1973), pp. 2300-2308.
Pitzer, K.S. and G. Mayorga, J. Solution Chem., Vol. 3, (1974), p. 539.
Pitzer, K.S., J.R. Peterson, and L.F. Silvester, "Thermodynamics of
Electrolytes. IX. Rare Earth Chlorides, Nitrates, and Perchlorates, "J. Solution
Chem., Vol. 7, No. 1, (1978), pp. 45-56.
Pitzer, K.S., R.N. Roy, and L.F. Silvester, "Thermodynamics of Electrolytes 7
Sulfuric Acid," J. Am. Chem. Soc., Vol. 99, No. 15, (1977), pp. 4930-4936.
Pitzer, K.S. and L.F. Silvester, J. Solution Chem., Vol. 5, (1976), p. 269.
Silvester, L.F. and K.S. Pitzer, "Thermodynamics of Electrolytes 8 High-
Temperature Properties, Including Enthalpy and Heat Capacity, With
Application to Sodium Chloride," J. Phys. Chem., Vol. 81, No. 19, (1977), pp.
1822-1828.

Polynomial Activity Coefficient


This model represents activity coefficient as an empirical function of
composition and temperature. It is used frequently in metallurgical
applications where multiple liquid and solid solution phases can exist.
The equation is:

Where:
Ai =

Bi =

Ci =

Di =

Ei =

For any component i, the value of the activity coefficient can be fixed:

2 Thermodynamic Property Models 133


γi = fi
This model is not part of any property method. To use it:
3. On the Properties | Specifications sheet, specify an activity coefficient
model, such as NRTL.
4. Click the Properties | Property Methods folder.
5. In the Object Manager, click New.
6. In the Create New ID dialog box, enter a name for the new method.
7. In the Base Property Method field, select NRTL.
8. Click the Models tab.
9. Change the Model Name for GAMMA from GMRENON to GMPOLY.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
GMPLYP/1 ai1 0 x — — —
GMPLYP/2 ai2 0 x — — —
GMPLYP/3 ai3 0 x — — —
GMPLYP/4 bi1 0 x — — —
GMPLYP/5 bi2 0 x — — —
GMPLYP/6 bi3 0 x — — —
GMPLYP/7 ci1 0 x — — —
GMPLYP/8 ci2 0 x — — —
GMPLYP/9 ci3 0 x — — —
GMPLYP/10 di1 0 x — — —
GMPLYP/11 di2 0 x — — —
GMPLYP/12 di3 0 x — — —
GMPLYP/13 ei1 0 x — — —
GMPLYP/14 ei2 0 x — — —
GMPLYP/15 ei3 0 x — — —
GMPLYO fi — x — — —

Note: If you specify GMPLYP on the Properties | Parameters | Pure


Component | T-Dependent sheet, you can only enter the first 12 elements.
If you want to specify values for elements 13 to 15, you should go to the
Flowsheeting Options | Add-Input | Add After sheet in Aspen Plus or the
Add-Input | Add-Input | Add After sheet in Aspen Properties, and enter
the values of all 15 elements as in the following example:
PROP-DATA GMPLYP-1
IN-UNITS SI
PROP-LIST GMPLYP
PVAL WATER 0.0 1.5 0.0 &
0.0 0.0 0.0 &
0.0 0.0 0.0 &
0.0 0.0 0.0 &
0.0 16. 0.0

134 2 Thermodynamic Property Models


Redlich-Kister
This model calculates activity coefficients. It is a polynomial in the difference
between mole fractions in the mixture. It can be used for liquid and solid
mixtures (mixed crystals).
The equation is:

Where:
nc = Number of components
A1,ij = aij / T + bij
A2,ij = cij / T + dij
A3,ij = eij / T + fij
A4,ij = gij / T + hij
A5,ij = mij / T + nij
An,ii = An,jj = 0.0
An,ji = An,ij(-1)(n-1)
An,kj = An,jk(-1)(n-1)
For any component i, the value of the activity coefficient can be fixed:

γi = vi
Parameter Name/ Symbol Default MDS Lower Upper Units
Element Limit Limit
GMRKTB/1 aij 0 x — — —
GMRKTB/2 bij 0 x — — —
GMRKTB/3 cij 0 x — — —
GMRKTB/4 dij 0 x — — —
GMRKTB/5 eij 0 x — — —
GMRKTB/6 fij 0 x — — —
GMRKTB/7 gij 0 x — — —
GMRKTB/8 hij 0 x — — —
GMRKTB/9 mij 0 x — — —
GMRKTB/10 nij 0 x — — —
GMRKTO vi — x — — —

Scatchard-Hildebrand
The Scatchard-Hildebrand model calculates liquid activity coefficients. It is
used in the CHAO-SEA property method and the GRAYSON property method.
The equation for the Scatchard-Hildebrand model is:

2 Thermodynamic Property Models 135


Where:
Aij =

ϕi =

Vm*,l =

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TC Tci — x 5.0 2000.0 TEMPERATURE
DELTA δi — x 103 105 SOLUPARAM

VLCVT1 Vi*,CVT — x 0.0005 1.0 MOLE-


VOLUME
GMSHVL Vi*,l x 0.01 1.0 MOLE-
VOLUME

GMSHXL kij 0.0 x -5 5 —

Three-Suffix Margules
This model can be used to describe the excess properties of liquid and solid
solutions. It does not find much use in chemical engineering applications, but
is still widely used in metallurgical applications. Note that the binary
parameters for this model do not have physical significance.
The equation is:

Where kij is a binary parameter:

For any component i, the value of the activity coefficient can be fixed:

γi = di
Parameter Name/ Symbol Default MDS Lower Upper Units
Element Limit Limit
GMMRGB/1 aij 0 x — — TEMPERATURE
GMMRGB/2 bij 0 x — — —
GMMRGB/3 cij 0 x — — —

136 2 Thermodynamic Property Models


Parameter Name/ Symbol Default MDS Lower Upper Units
Element Limit Limit
GMMRGO di — x — — —

References
M. Margules, "Über die Zusammensetzung der gesättigten Dämpfe von
Mischungen," Sitzungsber. Akad. Wiss. Vienna, Vol. 104, (1895), p. 1293.
D.A. Gaskell, Introduction to Metallurgical Thermodyanics, 2nd ed., (New
York: Hemisphere Publishing Corp., 1981), p. 360.
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987).

UNIFAC Activity Coefficient Model


The UNIFAC model calculates liquid activity coefficients for the following
property methods: UNIFAC, UNIF-HOC, and UNIF-LL. Because the UNIFAC
model is a group-contribution model, it is predictive. All published group
parameters and group binary parameters are stored in the Aspen Physical
Property System.
The equation for the original UNIFAC liquid activity coefficient model is made
up of a combinatorial and residual term:

ln γ = ln γic + ln γir
ln γic =

Where the molecular volume and surface fractions are:

and
Where nc is the number of components in the mixture. The coordination
number z is set to 10. The parameters ri and qi are calculated from the group
volume and area parameters:

and

Where νki is the number of groups of type k in molecule i, and ng is the


number of groups in the mixture.
The residual term is:

2 Thermodynamic Property Models 137


Γk is the activity coefficient of a group at mixture composition, and Γki is the
activity coefficient of group k in a mixture of groups corresponding to pure i.
The parameters Γk and Γki are defined by:

With:

And:

The parameter Xk is the group mole fraction of group k in the liquid:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
UFGRP (k,νk, m, νm, ...) — — — — —

GMUFQ Qk — — — — —
GMUFR Rk — — — — —
GMUFB bkn — — — — TEMPERATURE

The parameter UFGRP stores the UNIFAC functional group number and
number of occurrences of each group. UFGRP is stored in the Aspen Physical
Property System pure component databank for most components. For
nondatabank components, enter UFGRP on the Properties Molecular Structure
Functional Group sheet. See Physical Property Data, Chapter 3, for a list of
the UNIFAC functional groups.

UNIFAC-PSRK
The PSRK property method uses GMUFPSRK, the UNIFAC-PSRK model, which
is a variation on the standard UNIFAC model. UNIFAC-PSRK has special
groups defined for the light gases CO2, H2, NH3, N2, O2, CO, H2S, and argon,
and the group binary interaction parameters are temperature-dependent,
using the values in parameter UNIFPS, instead of the constant value from
GMUFB used above, so that:

138 2 Thermodynamic Property Models


Where a, b, and c are the three elements of UNIFPS.

References
Aa. Fredenslund, J. Gmehling and P. Rasmussen, "Vapor-Liquid Equilibria
using UNIFAC," (Amsterdam: Elsevier, 1977).
Aa. Fredenslund, R.L. Jones and J.M. Prausnitz, AIChE J., Vol. 21, (1975), p.
1086.
H.K. Hansen, P. Rasmussen, Aa. Fredenslund, M. Schiller, and J. Gmehling,
"Vapor-Liquid Equilibria by UNIFAC Group Contribution. 5 Revision and
Extension", Ind. Eng. Chem. Res., Vol. 30, (1991), pp. 2352-2355.

UNIFAC (Dortmund Modified)


The UNIFAC modification by Gmehling and coworkers (Weidlich and
Gmehling, 1987; Gmehling et al., 1993), is slightly different in the
combinatorial part. It is otherwise unchanged compared to the original
UNIFAC:

With:

The temperature dependency of the interaction parameters is:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
UFGRPD (k,νk, m, νm, ...) — — — — —

GMUFDQ Qk — — — — —
GMUFDR Rk — — — — —
UNIFDM/1 amn,1 0 — — — TEMPERATURE
UNIFDM/2 amn,2 0 — — — TEMPERATURE
UNIFDM/3 amn,3 0 — — — TEMPERATURE

The parameter UFGRPD stores the group number and the number of
occurrences of each group. UFGRPD is stored in the Aspen Physical Property
System pure component databank. For nondatabank components, enter
UFGRPD on the Properties Molecular Structure Functional Group sheet. See
Physical Property Data, Chapter 3, for a list of the Dortmund modified UNIFAC
functional groups.

2 Thermodynamic Property Models 139


References
U. Weidlich and J. Gmehling, "A Modified UNIFAC Model 1. Prediction of VLE,
hE and ," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 1372–1381.
J. Gmehling, J. Li, and M. Schiller, "A Modified UNIFAC Model. 2. Present
Parameter Matrix and Results for Different Thermodynamic Properties," Ind.
Eng. Chem. Res., Vol. 32, (1993), pp. 178–193.

UNIFAC (Lyngby Modified)


The equations for the "temperature-dependent UNIFAC" (Larsen et al., 1987)
are similar to the original UNIFAC:

Volume fractions are modified:

With:

Where Γk and Γki have the same meaning as in the original UNIFAC, but
defined as:

With:

140 2 Thermodynamic Property Models


The temperature dependency of a is described by a function instead of a
constant:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
UFGRPL (k,νk, m, νm, ...) — — — — —

GMUFLQ Qk — — — — —
GMUFLR Rk — — — — —
UNIFLB/1 amn,1 0 — — — TEMPERATURE
UNIFLB/2 amn,2 0 — — — TEMPERATURE
UNIFLB/3 amn,3 0 — — — TEMPERATURE

The parameter UFGRPL stores the modified UNIFAC functional group number
and the number of occurrences of each group. UFGRPL is stored in the Aspen
Physical Property System pure component databank. For nondatabank
components, enter UFGRP on the Properties | Molecular Structure |
Functional Group sheet. See Physical Property Data, Chapter 3, for a list of
the Larsen modified UNIFAC functional groups.
Reference: B. Larsen, P. Rasmussen, and Aa. Fredenslund, "A Modified
UNIFAC Group-Contribution Model for Prediction of Phase Equilibria and Heats
of Mixing," Ind. Eng. Chem. Res., Vol. 26, (1987), pp. 2274 – 2286.

UNIQUAC Activity Coefficient Model


The UNIQUAC model calculates liquid activity coefficients for these property
methods: UNIQUAC, UNIQ-2, UNIQ-HOC, UNIQ-NTH, and UNIQ-RK. It is
recommended for highly non-ideal chemical systems, and can be used for VLE
and LLE applications. This model can also be used in the advanced equations
of state mixing rules, such as Wong-Sandler and MHV2.
The equation for the UNIQUAC model is:

Where:
θi =

θi ' =

Φi =

2 Thermodynamic Property Models 141


li =

ti ' =

τij =

z = 10
aij, bij, cij, and dij are unsymmetrical. That is, aij may not be equal to aji, etc.
Absolute temperature units are assumed for the binary parameters aij, bij, cij,
dij, and eij.
can be determined from VLE and/or LLE data regression. The Aspen Physical
Property System has a large number of built-in parameters for the UNIQUAC
model. The binary parameters have been regressed using VLE and LLE data
from the Dortmund Databank. The binary parameters for VLE applications
were regressed using the ideal gas, Redlich-Kwong, and Hayden-O'Connell
equations of state. See Physical Property Data, Chapter 1, for details.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
GMUQR ri — x — — —
GMUQQ qi — x — — —
GMUQQ1 qi' q x — — —
UNIQ/1 aij 0 x -50.0 50.0 —
UNIQ/2 bij 0 x -15000.0 15000.0 TEMPERATURE
UNIQ/3 cij 0 x — — TEMPERATURE
UNIQ/4 dij 0 x — — TEMPERATURE
UNIQ/5 Tlower 0K x — — TEMPERATURE
UNIQ/6 Tupper 1000 K x — — TEMPERATURE
UNIQ/7 eij 0 x — — TEMPERATURE

Absolute temperature units are assumed for elements 2 through 4 and 7 of


UNIQ.
The UNIQ-2 property method uses data set 2 for UNIQ. All other UNIQUAC
methods use data set 1.

References
D.S. Abrams and J.M. Prausnitz, "Statistical Thermodynamics of liquid
mixtures: A new expression for the Excess Gibbs Energy of Partly or
Completely Miscible Systems," AIChE J., Vol. 21, (1975), p. 116.
A. Bondi, "Physical Properties of Molecular Crystals, Liquids and Gases," (New
York: Wiley, 1960).
Simonetty, Yee and Tassios, "Prediction and Correlation of LLE," Ind. Eng.
Chem. Process Des. Dev., Vol. 21, (1982), p. 174.

142 2 Thermodynamic Property Models


Van Laar Activity Coefficient Model
The Van Laar model (Van Laar 1910) calculates liquid activity coefficients for
the property methods: VANLAAR, VANL-2, VANL-HOC, VANL-NTH, and VANL-
RK. It can be used for highly nonideal systems.

Where:
zi =

Ai =

Bi =

Ci =

Aij =

Cij =

Cij = Cji
Aii = Bii = Cii = 0
aij and bij are unsymmetrical. That is, aij may not be equal to aji, and bij may
not be equal to bji.
Parameters Symbol Default MDS Lower Limit Upper Units
Name/Element Limit
VANL/1 aij 0 x -50.0 50.0 —
VANL/2 bij 0 x -15000.0 15000.0 TEMPERATURE
VANL/3 cij 0 x -50.0 50.0 —
VANL/4 dij 0 x -15000.0 15000.0 TEMPERATURE

The VANL-2 property method uses data set 2 for VANL. All other Van Laar
methods use data set 1.

References
J.J. Van Laar, "The Vapor Pressure of Binary Mixtures," Z. Phys. Chem., Vol.
72, (1910), p. 723.
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed. (New York: McGraw-Hill, 1987).

2 Thermodynamic Property Models 143


Wagner Interaction Parameter
The Wagner Interaction Parameter model calculates activity coefficients. This
model is used for dilute solutions in metallurgical applications.
The relative activity coefficient with respect to the reference activity
coefficient of a solute i (in a mixture of solutes i, j, and l and solvent A) is:

Where:

The parameter γiref is the reference activity coefficient of solute i:

kij is a binary parameter:

For any component i, the value of the activity coefficient can be fixed:

γi = gi
This model is recommended for dilute solutions.
Parameter Name/ Symbol Default MDS Lower Upper Units
Element Limit Limit
GMWIPR/1 ai 0 x — — TEMPERATURE
GMWIPR/2 bi 0 x — — —
GMWIPR/3 ci 0 x — — —
GMWIPB/1 dij 0 x — — TEMPERATURE
GMWIPB/2 eij 0 x — — —
GMWIPB/3 fij 0 x — — —
GMWIPO gi — x — — —
GMWIPS — 0 x — — —

GMWIPS is used to identify the solvent component. You must set GMWIPS to
1.0 for the solvent component. This model allows only one solvent.

References
A.D. Pelton and C. W. Bale, "A Modified Interaction Parameter Formalism for
Non-Dilute Solutions," Metallurgical Transactions A, Vol. 17A, (July 1986),
p. 1211.

144 2 Thermodynamic Property Models


Wilson Activity Coefficient Model
The Wilson model calculates liquid activity coefficients for the following
property methods: WILSON, WILS2, WILS-HOC, WILS-NTH, WILS-RK, WILS-
HF, WILS-LR, and WILS-GLR. It is recommended for highly nonideal systems,
especially alcohol-water systems. It can also be used in the advanced
equation-of-state mixing rules, such as Wong-Sandler and MHV2. This model
cannot be used for liquid-liquid equilibrium calculations.
The equation for the Wilson model is:

Where:

ln Aij =

The extended form of ln Aij provides more flexibility in fitting phase


equilibrium and enthalpy data. aij, bij, cij, dij, and eij are unsymmetrical. That
is, aij may not be equal to aji, etc.
The binary parameters aij, bij, cij, dij, and eij must be determined from data
regression or VLE and/or heat-of-mixing data. The Aspen Physical Property
System has a large number of built-in binary parameters for the Wilson
model. The binary parameters have been regressed using VLE data from the
Dortmund Databank. The binary parameters were regressed using the ideal
gas, Redlich-Kwong, and Hayden-O'Connell equations of state. See Physical
Property Data, Chapter 1, for details.
Parameter Symbol Default MDS Lower Limit Upper Units
Name/Element Limit
WILSON/1 aij 0 x -50.0 50.0 —
WILSON/2 bij 0 x -15000.0 15000.0 TEMPERATURE
††
WILSON/3 cij 0 x -— — TEMPERATURE
††
WILSON/4 dij 0 x — — TEMPERATURE
††
WILSON/5 Tlower 0K x — — TEMPERATURE
WILSON/6 Tupper 1000 K x — — TEMPERATURE
WILSON/7 eij 0 x — — TEMPERATURE
††

The WILS-2 property method uses data set 2 for WILSON. All other Wilson
methods use data set 1.
† In the original formulation of the Wilson model, aij = ln Vj/Vi, cij = dij = eij =
0, and
bij = -(λij - λii)/R, where Vj and Vi are pure component liquid molar volume at
25°C.
†† If any of biA, ciA, and eiA are non-zero, absolute temperature units are
assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are

2 Thermodynamic Property Models 145


interpreted in input units. The temperature limits are always interpreted in
input units.

References
G.M. Wilson, J. Am. Chem. Soc., Vol. 86, (1964), p. 127.

Wilson Model with Liquid Molar Volume


This Wilson model (used in the method WILS-VOL) calculates liquid activity
coefficients using the original formulation of Wilson (Wilson 1964) except that
liquid molar volume is calculated at system temperature, instead of at 25°C.
It is recommended for highly nonideal systems, especially alcohol water
systems. It can be used in any activity coefficient property method or in the
advanced equation of state mixing rules, such as Wong Sandler and MHV2.
This model cannot be used for liquid liquid equilibrium calculations.
The equation for the Wilson model is:

Where:

ln Aij =

Vj and Vi are pure component liquid molar volume at the system temperature
calculated using the Rackett/DIPPR/IK-CAPE model. The extended form of ln
Aij provides more flexibility in fitting phase equilibrium and enthalpy data. aij,
bij, cij, dij, and eij are unsymmetrical. That is, aij may not be equal to aji, etc.
The binary parameters aij, bij, cij, dij, and eij must be determined from data
regression of VLE and/or heat-of-mixing data. There are no built in binary
parameters for this model.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
WSNVOL/1 aij 0 x -50.0 50.0 —
WSNVOL/2 bij 0 x -15000.0 15000.0 TEMPERATURE
††
WSNVOL/3 cij 0 x -— — TEMPERATURE
††
WSNVOL/4 dij 0 x — — TEMPERATURE
††
WSNVOL/5 eij 0 x — — TEMPERATURE
††
WSNVOL/6 Tlower 0K x — — TEMPERATURE
WSNVOL/7 Tupper 1000 K x — — TEMPERATURE

Pure component parameters for the Rackett model/DIPPR/IK-CAPE are also


required.

146 2 Thermodynamic Property Models


† In the original formulation of the Wilson model, aij = cij = dij = eij = 0 and

. Vj and Vi are calculated at 25°C.


†† If any of biA, ciA, and eiA are non-zero, absolute temperature units are
assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are
interpreted in input units. The temperature limits are always interpreted in
input units.
Reference: G.M. Wilson, J. Am. Chem. Soc., Vol. 86, (1964), p. 127.

Vapor Pressure and Liquid


Fugacity Models
The Aspen Physical Property System has the following built-in vapor pressure
and liquid fugacity models. This section describes the vapor pressure and
liquid fugacity models available.
Model Type
Extended Antoine/Wagner/IK-CAPE Vapor pressure
API Sour Vapor pressure
Braun K-10 Vapor pressure
Chao-Seader Fugacity
Grayson-Streed Fugacity
Kent-Eisenberg Fugacity
Maxwell-Bonnell Vapor pressure
Solid Antoine Vapor pressure

Extended Antoine/Wagner/PPDS/IK-CAPE
Liquid Vapor Pressure Model
The Aspen Physical Property System has several submodels for calculating
vapor pressure of a liquid. It uses parameter THRSWT/3 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/3 is Then this equation is used
0 Extended Antoine
200 BARIN
301 Wagner
302 PPDS Modified Wagner
400 PML
401 IK-CAPE
501 NIST TDE Polynomial
502 NIST Wagner 25

2 Thermodynamic Property Models 147


Extended Antoine Equation
Parameters for many components are available for the extended Antoine
equation from the Aspen Physical Property System pure component databank.
This equation can be used whenever the parameter PLXANT is available.
The equation for the extended Antoine vapor pressure model is:

Extrapolation of ln pi*,l versus 1/T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/ Element Limit Limit
PLXANT/1 C1i x PRESSURE,
TEMPERATURE
PLXANT/2 C2i x TEMPERATURE

PLXANT/3, . . . , 7 C3i, ..., C7i 0 x TEMPERATURE

PLXANT/8 C8i 0 x TEMPERATURE

PLXANT/9 C9i 1000 x TEMPERATURE

If C5i, C6i, or C7i is non-zero, absolute temperature units are assumed for all
coefficients C1i through C7i. The temperature limits are always in user input
units.

Wagner Vapor Pressure Equation


The Wagner vapor pressure equation is the best equation for correlation. The
equation can be used if the parameter WAGNER is available:

Where:
Tri = T / Tci
pri*,l = pi*,l / pci
Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.

PPDS Modified Wagner Vapor Pressure Equation


The PPDS equation also uses the same parameter WAGNER as the standard
Wagner equation:

Where:
Tri = T / Tci
pri*,l = pi*,l / pci

148 2 Thermodynamic Property Models


Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
WAGNER/1 C1i x

WAGNER/2 C2i 0 x

WAGNER/3 C3i 0 x

WAGNER/4 C4i 0 x

WAGNER/5 C5i 0 x TEMPERATURE

WAGNER/6 C6i 1000 x TEMPERATURE

TC Tci TEMPERATURE

PC pci PRESSURE

NIST Wagner 25 Liquid Vapor Pressure Equation


This equation is the same as the PPDS Modified Wagner equation above, but
it uses parameter WAGNER25 instead of WAGNER, and it uses critical
properties from this parameter set also.

Where:
Tri = T / Tci
Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
WAGNER25/1 C1i x

WAGNER25/2 C2i 0 x

WAGNER25/3 C3i 0 x

WAGNER25/4 C4i 0 x

WAGNER25/5 ln pci 0 x

WAGNER25/6 Tci x TEMPERATURE

WAGNER25/7 Tlower 0 x TEMPERATURE

WAGNER25/8 Tupper 1000 x TEMPERATURE

IK-CAPE Vapor Pressure Equation


The IK-CAPE model is a polynomial equation. If the parameter PLPO is
available, the Aspen Physical Property System can use the IK-CAPE vapor
pressure equation:

2 Thermodynamic Property Models 149


Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PLPO/1 C1i X PRESSURE
TEMPERATURE
PLPO/2, ..., 10 C2i , ..., C10i 0 X TEMPERATURE

PLPO/11 C11i 0 X TEMPERATURE

PLPO/12 C12i 1000 X TEMPERATURE

PML Vapor Pressure Equations


The PML vapor pressure equations are modified versions of the Antoine and
Wagner equations. Each equation comes in two alternate forms, identical
except for the use of natural or base-10 logarithms. Parameter LNVPEQ/1
specifies the number of the equation used. Each equation uses a separate
parameter: LNVP1 for equation 1, LOGVP1 for 2, LNPR1 for 3, LOGPR1 for 4,
LNPR2 for 5, and LOGPR2 for 6.
Equation 1 (natural logarithm) and 2 (base 10 logarithm):

Equation 3 (natural logarithm) and 4 (base 10 logarithm):

Equation 5 (natural logarithm) and 6 (base 10 logarithm):

Where:
Tri = T / Tci
pri*,l = pi*,l / pci
LNVPEQ/2 and LNVPEQ/3 are the lower and upper temperature limits,
respectively.
In equations 1-4, if elements 4, 7, or 8 are non-zero, absolute temperature
units are assumed for all elements.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
LNVP1/1, ...,8 C1i, ..., C8i x PRESSURE
TEMPERATURE

150 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
LOGVP1/1, ..., 8 C1i, ..., C8i x PRESSURE
TEMPERATURE
LNPR1/1, ..., 8 C1i, ..., C8i x PRESSURE
TEMPERATURE
LOGPR1/1, ..., 8 C1i, ..., C8i x PRESSURE
TEMPERATURE
LNPR2/1,2 C1i, C2i x

LOGPR2/1,2 C1i, C2i x

LNVPEQ/1 (equation
number)
LNVPEQ/2 Tlower 0 X TEMPERATURE

LNVPEQ/3 Tupper 1000 X TEMPERATURE

TC Tci TEMPERATURE

PC pci PRESSURE

NIST TDE Polynomial for Liquid Vapor Pressure


This equation can be used for calculating vapor pressure when parameter
PLTDEPOL is available.

Linear extrapolation of ln pi*,l versus T occurs outside of temperature bounds.


If elements 2, 3, 6, or 8 are non-zero, absolute temperature units are
assumed for all elements.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
PLTDEPOL/1 C1i X

PLTDEPOL/2 C2i 0 X TEMPERATURE

PLTDEPOL/3 C3i 0 X

PLTDEPOL/4, ..., 8 C4i , ..., C8i 0 X TEMPERATURE

PLTDEPOL/9 Tlower 0 X TEMPERATURE

PLTDEPOL/10 Tupper 1000 X TEMPERATURE

References
Reid, Prausnitz, and Poling, The Properties of Gases and Liquids, 4th ed.,
(New York: McGraw-Hill, 1987).
Harlacher and Braun, "A Four-Parameter Extension of the Theorem of
Corresponding States," Ind. Eng. Chem. Process Des. Dev., Vol. 9, (1970), p.
479.

2 Thermodynamic Property Models 151


W. Wagner, Cryogenics, Vol. 13, (1973), pp. 470-482.
D. Ambrose, M. B. Ewing, N. B. Ghiassee, and J. C. Sanchez Ochoa "The
ebulliometric method of vapor-pressure measurement: vapor pressures of
benzene, hexafluorobenzene, and naphthalene," J. Chem. Thermodyn. 22
(1990), p. 589.

API Sour Model


The API Sour model is based on the API sour water model for correlating the
ammonia, carbon dioxide, and hydrogen sulfide volatilities from aqueous sour
water system. The model assumes aqueous phase chemical equilibrium
reactions involving CO2, H2S, and NH3.
The model is applicable from 20 C to 140 C. The authors developed the model
using available phase equilibrium data and reported average errors between
the model and measured partial pressure data as follows
Compound Average Error, %
Up to 60 C Above 60 C

Ammonia 10 36
Carbon dioxide 11 24
Hydrogen sulfide 12 29

Detail of the model is described in the reference below and is too involved to
be reproduced here.

Reference
New Correlation of NH3, CO2, and H2S Volatility Data from Aqueous Sour
Water Systems, API Publication 955, March 1978 (American Petroleum
Institute).

Braun K-10 Model


The BK10 model uses the Braun K-10 K-value correlations, which were
developed from the K10 charts (K-values at 10 psia) for both real and pseudo
components. The form of the equation used is an extended Antoine vapor
pressure equation with coefficients specific to real components and pseudo
component boiling ranges.
This method is strictly applicable to heavy hydrocarbons at low pressures.
However, our model includes coefficients for a large number of hydrocarbons
and light gases. For pseudocomponents the model covers boiling ranges 450
– 700 K (350 – 800F). Heavier fractions can also be handled using the
methods developed by AspenTech.

References
B.C. Cajander, H.G. Hipkin, and J.M. Lenoir, "Prediction of Equilibrium Ratios
from Nomograms of Improved Accuracy," Journal of Chemical Engineering
Data, vol. 5, No. 3, July 1960, p. 251-259.

152 2 Thermodynamic Property Models


J.M. Lenoir, "Predict K Values at Low Temperatures, part 1," Hydrocarbon
Processing, p. 167, September 1969.
J.M. Lenoir, "Predict K Values at Low Temperatures, part 2," Hydrocarbon
Processing, p. 121, October 1969.

Chao-Seader Pure Component Liquid


Fugacity Model
The Chao-Seader model calculates pure component fugacity coefficient, for
liquids. It is used in the CHAO-SEA property method. This is an empirical
model with the Curl-Pitzer form. The general form of the model is:

Where:
=

Parameter Symbol Default MDS Lower Limit Upper Units


Name/Element Limit
TC Tci — — 5.0 2000.0 TEMPERATURE
PC pci — — 105 108 PRESSURE
OMEGA ωi — — -0.5 2.0 —

References
K.C. Chao and J.D. Seader, "A General Correlation of Vapor-Liquid Equilibria
in Hydrocarbon Mixtures," AIChE J., Vol. 7, (1961), p. 598.

Grayson-Streed Pure Component Liquid


Fugacity Model
The Grayson-Streed model calculates pure component fugacity coefficients for
liquids, and is used in the GRAYSON/GRAYSON2 property methods. It is an
empirical model with the Curl-Pitzer form. The general form of the model is:

Where:

Parameter Symbol Default MDS Lower Limit Upper Units


Name/Element Limit
TC Tci — — 5.0 2000.0 TEMPERATURE
5 8
PC pci — — 10 10 PRESSURE
OMEGA ωi — — -0.5 2.0 —

2 Thermodynamic Property Models 153


References
H.G. Grayson and C.W. Streed, Paper 20-PO7, Sixth World Petroleum
Conference, Frankfurt, June 1963.

Kent-Eisenberg Liquid Fugacity Model


The Kent-Eisenberg model calculates liquid mixture component fugacity
coefficients and liquid enthalpy for the AMINES property method.
The chemical equilibria in H2S + CO2 + amine systems are described using
these chemical reactions:

Where:
R' = Alcohol substituted alkyl groups
The equilibrium constants are given by:

The chemical equilibrium equations are solved simultaneously with the


balance equations. This obtains the mole fractions of free H2S and CO2 in
solution. The equilibrium partial pressures of H2S and CO2 are related to the
respective free concentrations by Henry's constants:

The apparent fugacities and partial molar enthalpies, Gibbs energies and
entropies of H2S and CO2 are calculated by standard thermodynamic
relationships. The chemical reactions are always considered.

154 2 Thermodynamic Property Models


The values of the coefficients for the seven equilibrium constants (A1i, ... A5i)
and for the two Henry's constants B1i and B2i are built into the Aspen Physical
Property System. The coefficients for the equilibrium constants were
determined by regression. All available data for the four amines were used:
monoethanolamine, diethanolamine, disopropanolamine and diglycolamine.
You are not required to enter any parameters for this model.

References
R.L. Kent and B. Eisenberg, Hydrocarbon Processing, (February 1976),
pp. 87-92.

Maxwell-Bonnell Vapor Pressure Model


The Maxwell-Bonnell model calculates vapor pressure using the Maxwell-
Bonnell vapor pressure correlation for all hydrocarbon pseudo-components as
a function of temperature. This is an empirical correlation based on API
procedure 5A1.15, 5A1.13. This model is used in property method MXBONNEL
for calculating vapor pressure and liquid fugacity coefficients (K-values).

References
API procedure 5A1.15 and 5A1.13.

Solid Antoine Vapor Pressure Model


The vapor pressure of a solid can be calculated using the Antoine equation.
Parameters for some components are available for the extended Antoine
equation from the Aspen Physical Property System pure component databank.
This equation can be used whenever the parameter PSANT is available.
The equation for the solid Antoine vapor pressure model is:

Extrapolation of ln pi*,s versus 1/T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Limit Upper Units
Name/ Limit
Element
PSANT/1 C1i — x — — PRESSURE,
TEMPERATURE
PSANT/2 C2i — x — — TEMPERATURE
PSANT/3 C3i 0 x — — TEMPERATURE
PSANT/4 C4i 0 x — — TEMPERATURE
PSANT/5 C5i 1000 x — — TEMPERATURE

2 Thermodynamic Property Models 155


DIPPR/Watson/PPDS/IK-CAPE
Heat of Vaporization Model
The Aspen Physical Property System has several submodels for calculating
pure component heat of vaporization. It uses parameter THRSWT/4 to
determine which submodel is used. See Pure Component Temperature-
Dependent Properties for details.
If THRSWT/4 is Then this equation is used
0 Watson
106 DIPPR
301 PPDS
401 IK-CAPE
505 NIST TDE Watson equation

DIPPR Heat of Vaporization Equation


The DIPPR equation is used to calculate heat of vaporization when THRSWT/4
is set to 106. (Other DIPPR equations may sometimes be used. See Pure
Component Temperature-Dependent Properties for details.)
The equation for the DIPPR heat of vaporization model is:

Where:
Tri = T / Tci

Note: Reduced temperature Tr is always calculated using absolute


temperature units.

Linear extrapolation of ΔvapHi* versus T occurs outside of temperature bounds,


using the slope at the temperature bound, except that ΔvapHi* is zero for

.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DHVLDP/1 C1i — x — — MOLE-ENTHALPY
DHVLDP/2, ..., 5 C2i, ..., C5i 0 x — — —
DHVLDP/6 C6i 0 x — — TEMPERATURE
DHVLDP/7 C7i 1000 x — — TEMPERATURE
TC Tci — — 5.0 2000.0 TEMPERATURE

156 2 Thermodynamic Property Models


Watson Heat of Vaporization Equation
The Watson equation is used to calculate heat of vaporization when
THRSWT/4 is set to 0. See Pure Component Temperature-Dependent
Properties for details.
The equation for the Watson model is:

Where:

ΔvapHi*(T1) = Heat of vaporization at temperature T1

Linear extrapolation of ΔvapHi* versus T occurs below the minimum


temperature bound, using the slope at the temperature bound.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
TC Tci — 5.0 2000.0 TEMPERATURE
4 8
DHVLWT/1 ΔvapHi*(T1) — 5x10 5x10 MOLE-ENTHALPY

DHVLWT/2 T1 — 4.0 3500.0 TEMPERATURE


DHVLWT/3 ai 0.38 -2.0 2.0 —
DHVLWT/4 bi 0 -2.0 2.0 —
DHVLWT/5 Tmin 0 0.0 1500.0 TEMPERATURE

PPDS Heat of Vaporization Equation


The PPDS equation is used to calculate heat of vaporization when THRSWT/4
is set to 301. See Pure Component Temperature-Dependent Properties for
details.
The equation for the PPDS model is:

where R is the gas constant.

Linear extrapolation of ΔvapHi* versus T occurs outside of temperature bounds,


using the slope at the temperature bound.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TC Tci — 5.0 2000.0 TEMPERATURE
DHVLDS/1 C1i — — — — —
DHVLDS/2 C2i 0 — — — —
DHVLDS/3 C3i 0 — — — —
DHVLDS/4 C4i 0 — — — —
DHVLDS/5 C5i 0 — — — —

2 Thermodynamic Property Models 157


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DHVLDS/6 C6i 0 — — TEMPERATURE
DHVLDS/7 C7i 1000 — — TEMPERATURE

IK-CAPE Heat of Vaporization Equation


The IK-CAPE equation is used to calculate heat of vaporization when
THRSWT/4 is set to 401. See Pure Component Temperature-Dependent
Properties for details.
The equation for the IK-CAPE model is:

Linear extrapolation of ΔvapHi* versus T occurs outside of temperature bounds,


using the slope at the temperature bound
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DHVLPO/1 C1i — X — — MOLE-
ENTHALPY
DHVLPO/2, ..., 10C2i, ..., C10i 0 X — — MOLE-
ENTHALPY
TEMPERATURE
DHVLPO/11 C11i 0 X — — TEMPERATURE
DHVLPO/12 C12i 1000 X — — TEMPERATURE

NIST TDE Watson Heat of Vaporization


Equation
The NIST TDE Watson equation is used to calculate heat of vaporization when
THRSWT/4 is set to 505. See Pure Component Temperature-Dependent
Properties for details.
The equation is:

Linear extrapolation of ΔvapHi* versus T occurs outside of temperature bounds,


using the slope at the temperature bound
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DHVLTDEW/1 C1i — X — — —

158 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DHVLTDEW/2, 3, C2i, C3i, C4i 0 X — — —
4
DHVLTDEW/5 Tci — X — — TEMPERATURE
DHVLTDEW/6 nTerms 4 X — — —
DHVLTDEW/7 Tlower 0 X — — TEMPERATURE
DHVLTDEW/8 Tupper 1000 X — — TEMPERATURE

Clausius-Clapeyron Equation
The Aspen Physical Property System can calculate heat of vaporization using
the Clausius Clapeyron equation:

Where:
= Slope of the vapor pressure curve calculated from the Extended
Antoine equation

Vi*,v = Vapor molar volume calculated from the Redlich Kwong


equation of state
Vi*,l = Liquid molar volume calculated from the Rackett equation
For parameter requirements, see Extended Antoine/Wagner, the Rackett
model, and Redlich Kwong.

Molar Volume and Density


Models
The Aspen Physical Property System has the following built-in molar volume
and density models available. This section describes the molar volume and
density models.
Model Type
API Liquid Volume Liquid volume
Brelvi-O'Connell Partial molar liquid
volume of gases
Clarke Aqueous Electrolyte Volume Liquid volume
COSTALD Liquid Volume Liquid volume
Debye-Hückel Volume Electrolyte liquid volume
Liquid Constant Molar Volume Model Liquid volume
Rackett/DIPPR/PPDS/IK-CAPE Liquid Molar Liquid volume/liquid
Volume density

2 Thermodynamic Property Models 159


Model Type
Rackett/Campbell-Thodos Mixture Liquid Liquid volume
Volume
Modified Rackett Liquid volume
Aspen/DIPPR/IK-CAPE Solids Volume Solid volume
Liquid Volume Quadratic Mixing Rule Liquid volume

API Liquid Volume


This model calculates liquid molar volume for a mixture, using the API
procedure and the Rackett model. Ideal mixing is assumed:

Where:
xp = Mole fraction of pseudocomponents
xr = Mole fraction of real components
For pseudocomponents, the API procedure is used:

Where:
fcn = A correlation based on API Figure 6A3.5 (API Technical Data Book,
Petroleum Refining, 4th edition)
At high density, the Ritter equation is used (adapted from Ritter, Lenoir, and
Schweppe, Petrol. Refiner 37 [11] 225 (1958)):

Where SG is the specific gravity, Tb is the mean average boiling point in


Rankine, T is the temperature of the system in Rankine, and the mass volume
is produced in units of cubic feet per pound-mass.
For real components, the mixture Rackett model is used:

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
See the Rackett model for descriptions.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TB Tb — — 4.0 2000.0 TEMPERATURE
API API — — -60.0 500.0 —

160 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TC Tc — — 5.0 2000.0 TEMPERATURE
5 8
PC pc — — 10 10 PRESSURE
RA
RKTZRA Z ZC — 0.1 0.5 —

Brelvi-O'Connell
The Brelvi-O'Connell model calculates partial molar volume of a supercritical
component i at infinite dilution in pure solvent A. Partial molar volume at
infinite dilution is required to compute the effect of pressure on Henry's
constant. (See Henry's Constant.)
The general form of the Brelvi-O'Connell model is:

Where:
i = Solute or dissolved-gas component
A = Solvent component
The liquid molar volume of solvent is obtained from the Rackett model:

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TC TcA — — 5.0 2000.0 TEMPERATURE
5 8
PC pcA — — 10 10 PRESSURE
RKTZRA ZARA ZC x 0.1 1.0 —
VLBROC/1 ViBO VC x -1.0 1.0 MOLE-VOLUME
VLBROC/2 — 0 x -0.1 0.1 TEMPERATURE

References
S.W. Brelvi and J.P. O'Connell, AIChE J., Vol. 18, (1972), p. 1239.
S.W. Brelvi and J.P. O'Connell, AIChE J., Vol. 21, (1975), p. 157.

Clarke Aqueous Electrolyte Volume


The Clarke model calculates liquid molar volume for electrolytes solutions.
The model is applicable to mixed solvents and is based on:
• Molar volume of molecular solvents (equation 2)

2 Thermodynamic Property Models 161


• The relationship between the partial molar volume of an electrolyte and its
mole fraction in the solvent (equation 4)
All quantities are expressed in terms of apparent components.
If option code 1 is set to 1, the liquid volume quadratic mixing rule is used
instead. The default option uses this equation to calculate the liquid molar
volume for electrolyte solutions:
(1)

Where:
Vml = Liquid molar volume for electrolyte solutions.
Vsl = Liquid molar volume for solvent mixtures.
Vel = Liquid molar volume for electrolytes.

Apparent Component Approach


For molecular solvents, the liquid molar volume is calculated by:
(2)

Where:
xw = Mole fraction of water
Vw* = Molar volume of water from the steam table.
xnws = Sum of the mole fractions of all non-water
solvents.
Vnwsl = Liquid molar volume for the mixture of all non-
water solvents. It is calculated using the
Rackett equation.
For electrolytes:
(3)

(4)

(5)

Where:
xca = Apparent mole fraction of electrolyte ca
Vca = Liquid molar volume for electrolyte ca
The mole fractions xca are reconstituted arbitrarily from the true ionic
concentrations, even if you use the apparent component approach. This
technique is explained in Electrolyte Calculation in Physical Property Methods.

162 2 Thermodynamic Property Models


The result is that electrolytes are generated from all possible combinations of
ions in solution. The following equation is consistently applied to determine
the amounts of each possible apparent electrolyte nca:
(6)

Where:
nca = Number of moles of apparent electrolyte ca
zc = Charge of c
zfactor = zc if c and a have the same number of
charges; otherwise 1.
nc = Number of moles of cation c
na = Number of moles of anion a
For example: given an aqueous solution of Ca2+, Na+, SO42-, Cl- four
electrolytes are found: CaCl2, Na2SO4, CaSO4, and NaCl. The Clarke
parameters of all four electrolytes are used. You can rely on the default,
which calculates the Clarke parameters from ionic parameters. Otherwise, you
must enter parameters for any electrolytes that may not exist in the
components list. If you do not want to use the default, the first step in using
the Clarke model is to add any needed components for electrolytes not in the
components list.

True Component Approach


The true molar volume is obtained from the apparent molar volume:
(7)

Where:
Vml,t = Liquid volume per number of true species
Vml,a = Liquid volume per number of apparent species, Vml
of equation 1
na = Number of apparent species
t
n = Number of true species
The apparent molar volume is calculated as explained in the preceding
subsection.

Temperature Dependence
The temperature dependence of the molar volume of the solution is
approximately equal to the temperature dependence of the molar volume of
the solvent mixture:

2 Thermodynamic Property Models 163


(8)

Where Vml(298.15K) is calculated from equation 1.


Parameter Applicable Symbol Default Units
Name/Element Components
VLCLK/1 Cation-Anion † MOLE-VOLUME

VLCLK/2 Cation-Anion Aca 0.020 MOLE-VOLUME

†If VLCLK/1 is missing, it is calculated based on VLBROC and CHARGE. If


VLBROC is missing, the default value of -0.12x10-2 is used.
See also Rackett/Campbell-Thodos Mixture Liquid Volume for additional
parameters used in the Rackett equation.

Reference
C.C. Chen, private communication.

COSTALD Liquid Volume


The equation for the COSTALD liquid volume model is:

Where:
δ
VmR,0 and VmR, are functions or Tr for

For , there is a linear interpolation between the liquid density at


Tr = 0.95 and the vapor density at Tr = 1.05. This model can be used to
calculate saturated and compressed liquid molar volume. The compressed
liquid molar volume is calculated using the Tait equation:

Where B and C are functions of T, ω, Tc, Pc and Psat is the saturated pressure
at T.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Mixing Rules:

164 2 Thermodynamic Property Models


Where:

To improve results, the Aspen Physical Property System uses a special


correlation for water when this model is used. Changing the VSTCTD and
OMGCTD parameters for water will not affect the results of the special
correlation.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TC Tci — — 5.0 2000.0 TEMPERATURE
*,CTD
VSTCTD Vr VC X 0.001 3.5 MOLE-VOLUME
OMGCTD ωr OMEGA X -0.5 2.0 —

References
R.W. Hankinson and G.H. Thomson, AIChE J., Vol. 25, (1979), p. 653.
G.H. Thomson, K.R. Brobst, and R.W. Hankinson, AIChE J., Vol. 28, (1982),
p. 4, p. 671.

Debye-Hückel Volume
The Debye-Hückel model calculates liquid molar volume for aqueous
electrolyte solutions.
The equation for the Debye-Hückel volume model is:

Where:

Vk is the molar volume for water and is calculated from the ASME steam
table.
Vk is calculated from the Debye-Hückel limiting law for ionic species. It is
assumed to be the infinite dilution partial volume for molecular solutes.

Where:
∞ = Partial molar ionic volume at infinite dilution
Vk
zk = Charge number of ion k
Av = Debye-Hückel constant for volume
b = 1.2

2 Thermodynamic Property Models 165


I =
the ionic strength, with
mk = Molarity of ion k
Av is computed as follows:

Where:

Aϕ = Debye-Hückel constant for the osmotic


coefficients (Pitzer, 1979)

ρw = Density of water (kg / m3)

εw = Dielectric constant of water (Fm-1), a function


of pressure and temperature (Bradley and
Pitzer, 1979)

Parameter Name Applicable Symbol Default Units


Components
VLBROC Ions, molecular Solutes Vk∞ 0 MOLE-VOLUME

References
D. J. Bradley, K. S. Pitzer, "Thermodynamics of Electrolytes," J. Phys. Chem.,
83 (12), 1599 (1979).
H.C. Helgeson and D.H. Kirkham, "Theoretical prediction of the
thermodynamic behavior of aqueous electrolytes at high pressure and
temperature. I. Thermodynamic/electrostatic properties of the solvent", Am.
J. Sci., 274, 1089 (1974).
K.S. Pitzer, "Theory: Ion Interaction Approach," Activity Coefficients in
Electrolyte Solutions, Pytkowicz, R. ed., Vol. I, (CRC Press Inc., Boca Raton,
Florida, 1979).

Liquid Constant Molar Volume Model


This model, VL0CONS, uses a constant value entered by the user as the pure
component liquid molar volume. It is not a function of temperature or
pressure. This is used with the solids handling property method for modeling
nonconventional solids.
Parameter Name Default MDS Units
VLCONS 1 x MOLE-VOLUME

166 2 Thermodynamic Property Models


Rackett/DIPPR/PPDS/IK-CAPE Liquid
Molar Volume
The Aspen Physical Property System has several submodels for calculating
liquid molar volume. It uses parameter THRSWT/2 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/2 is This equation is used And this parameter is used
0 Rackett RKTZRA
100-116 DIPPR DNLDIP
301 PPDS DNLPDS
401 IK-CAPE VLPO
503 NIST ThermoML DNLTMLPO
Polynomial
504 NIST TDE expansion DNLEXSAT
514 NIST TDE Rackett DNLRACK
515 NIST COSTALD DNLCOSTD

For liquid molar volume of mixtures, the Rackett mixture equation is always
used by default. This is not necessarily consistent with the pure component
molar volume or density. If you need consistency, select route VLMX26 on the
Properties | Property Methods form. This route calculates mixture molar
volume from the mole-fraction average of pure component molar volumes.
Many of these equations calculate density first, and return calculate liquid
molar volume based on that density:

DIPPR
DIPPR equation 105 is the default DIPPR equation for most substances:

This equation is similar to the Rackett equation.


DIPPR equation 116 is the default equation for water.

τ = 1 - T / Tc
Other DIPPR equations, such as equation 100, may be used for some
substances. Check the value of THRSWT/2 to determine the equation used.
See Pure Component Temperature-Dependent Properties for details about
DIPPR equations.

In either case, linear extrapolation of ρi*,l versus T occurs outside of


temperature bounds.

2 Thermodynamic Property Models 167


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DNLDIP/1 C1i — x — — MOLE-DENSITY †
DNLDIP/2 C2i 0 x — — †
DNLDIP/3 C3i Tci † x — — TEMPERATURE †
DNLDIP/4 C4i 0 x — — †
DNLDIP/5 C5i 0 x — — †
DNLDIP/6 C6i 0 x — — TEMPERATURE
DNLDIP/7 C7i 1000 x — — TEMPERATURE

† For equation 116, the units are MOLE-DENSITY for parameters DNLDIP/1
through DNLDIP/5 and the default for DNLDIP/3 is 0. For equation 105,
DNLDIP/5 is not used, and absolute temperature units are assumed for
DNLDIP/3.

PPDS
The PPDS equation is:

Linear extrapolation of ρi*,l versus T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —
VC Vci — — 0.001 3.5 MOLE-VOLUME
TC Tci — — 5.0 2000.0 TEMPERATURE
DNLPDS/1 C1i — — — — MASS-DENSITY
DNLPDS/2 C2i 0 — — — MASS-DENSITY
DNLPDS/3 C3i 0 — — — MASS-DENSITY
DNLPDS/4 C4i 0 — — — MASS-DENSITY
DNLPDS/5 C5i 0 x — — TEMPERATURE
DNLPDS/6 C6i 1000 x — — TEMPERATURE

IK-CAPE
The IK-CAPE equation is:

Linear extrapolation of Vi*,l versus T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VLPO/1 C1i — X — — MOLE-
VOLUME

168 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VLPO/2, ..., 10 C2i, ..., C10i 0 X — — MOLE-
VOLUME
TEMPERATURE
VLPO/11 C11i 0 X — — TEMPERATURE
VLPO/12 C12i 1000 X — — TEMPERATURE

NIST ThermoML Polynomial


This equation can be used when parameter DNLTMLPO is available.

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
DNLTMLPO/1 C1i — X — — MOLE-
DENSITY
DNLTMLPO/2, 3, C2i, C3i, C4i 0 X — — MOLE-
4 DENSITY
TEMPERATURE
DNLTMLPO/5 nTerms 4 X — — —
DNLTMLPO/6 0 X — — TEMPERATURE

DNLTMLPO/7 1000 X — — TEMPERATURE

Rackett
The Rackett equation is:

Where:
Tr = T / Tci

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
TC Tci — — 5.0 2000.0 TEMPERATURE
5 8
PC pci — — 10 10 PRESSURE
RKTZRA Zi*,RA ZC x 0.1 1.0 —

NIST TDE Rackett Parameters


This equation can be used when the parameter DNLRACK is available.

2 Thermodynamic Property Models 169


Linear extrapolation of Vi*,l versus T occurs outside of temperature bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
DNLRACK/1 Zc — x — — —
DNLRACK/2 n 2/7 x — — —
DNLRACK/3 Tci — x — — TEMPERATURE
DNLRACK/4 pci 0 x — — PRESSURE
DNLRACK/5 Tlower 0 x — — TEMPERATURE
DNLRACK/6 Tupper 1000 x — — TEMPERATURE

NIST COSTALD Parameters


This equation can be used when the parameter DNLCOSTD is available.

Linear extrapolation of Vi*,l versus T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
DNLCOSTD/1 Voi — x — — VOLUME
DNLCOSTD/2 Ω 0 x — — —

DNLCOSTD/3 Tci — x — — TEMPERATURE


DNLCOSTD/4 Tlower 0 x — — TEMPERATURE
DNLCOSTD/5 Tupper 1000 x — — TEMPERATURE

NIST TDE Expansion


This equation can be used when the parameter DNLEXSAT is available.

Linear extrapolation of Vi*,l versus T occurs outside of temperature bounds.

170 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
DNLEXSAT/1 ρci — x — — MOLE-
DENSITY
DNLEXSAT/2 C1i — x — — MOLE-
DENSITY
DNLEXSAT/3, C2i, ..., C6i 0 x — — MOLE-
..., DNLEXSAT/7 DENSITY
DNLEXSAT/8 Tci — x — — TEMPERATURE
DNLEXSAT/9 nTerms 6 x — — —
DNLEXSAT/10 Tlower 0 x — — TEMPERATURE
DNLEXSAT/11 Tupper 1000 x — — TEMPERATURE

References
H.G. Rackett, J.Chem. Eng. Data., Vol. 15, (1970), p. 514.
C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol. 17, (1972), p. 236.

Rackett/Campbell-Thodos Mixture Liquid


Volume
The Rackett equation calculates liquid molar volume for all activity coefficient
based and petroleum tuned equation of state based property methods. In the
last category of property methods, the equation is used in conjunction with
the API model. The API model is used for pseudocomponents, while the
Rackett model is used for real components. (See API Liquid Volume .)
Campbell-Thodos is a variation on the Rackett model which allows the
compressibility term Zi*,RA to vary with temperature.

Rackett
The equation for the Rackett model is:

Where:
Tc =

ZmRA =

2 Thermodynamic Property Models 171


Vcm =

Tr = T / Tc

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
TC Tci — — 5.0 2000.0 TEMPERATURE
PC pci — — 105 108 PRESSURE
VCRKT Vci VC x 0.001 3.5 MOLE-
VOLUME
RKTZRA Zi*,RA ZC x 0.1 1.0 —
RKTKIJ kij x -5.0 5.0 —

Campbell-Thodos
The Campbell-Thodos model uses the same equation and parameters as the
Rackett model, above, except that ZmRAis allowed to vary with temperature:
ZmRA =

Campbell-Thodos also uses separately-adjustable versions of the critical


parameters. Tmin and Tmax define the temperature range where the
equation is applicable.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
RACKET/1 R*Tci/Pci R*Tci/Pci — — — MOLE-
VOLUME
RACKET/2 Zi*,RA RKTZRA x 0.1 1.0 —
RACKET/3 di 0 x 0 0.11 —
RACKET/4 Tmin 0 x — — TEMPERATURE
RACKET/5 Tmax 1000 x — — TEMPERATURE

The Campbell-Thodos model is used when RACKET/3 is set to a value less


than 0.11. The default value, 2/7, indicates that the standard Rackett
equation should be used. When Campbell-Thodos is not used, RACKET/3
should be kept at its default value of 2/7 for all components.

References
H.G. Rackett, J.Chem, Eng. Data., Vol. 15, (1970), p. 514.
C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol. 17, (1972), p. 236.

172 2 Thermodynamic Property Models


Modified Rackett Liquid Molar Volume
The Modified Rackett equation improves the accuracy of liquid mixture molar
volume calculation by introducing additional parameters to compute the pure
component parameter RKTZRA and the binary parameter kij.
The equation for the Modified Rackett model is:

Where:
Tc =

kij =

ZmRA =

Zi*,RA =

Vcm =

Tr = T / Tc

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MRKZRA/1 ai RKTZRA x 0.1 0.5 —
MRKZRA/2 bi 0 x — — —
MRKZRA/3 ci 0 x — — —
MRKKIJ/1 Aij x — — —

MRKKIJ/2 Bij 0 x — — —
MRKKIJ/3 Cij 0 x — — —

References
H.G. Rackett, J.Chem, Eng. Data., Vol. 15, (1970), p. 514.
C.F. Spencer and R.P. Danner, J. Chem. Eng. Data, Vol. 17, (1972), p. 236.

2 Thermodynamic Property Models 173


Aspen/DIPPR/IK-CAPE Solid Molar Volume
The Aspen Physical Property System has several submodels for calculating
solid molar volume. It uses parameter THRSWT/1 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/1 is This equation is used And this parameter is
used
0 Aspen VSPOLY
100 DIPPR DNSDIP
401 IK-CAPE VSPO
503 NIST ThermoML DNSTMLPO
polynomial

Aspen Polynomial
The equation for the Aspen solids volume polynomial is:

Linear extrapolation of Vi*,s versus T occurs outside of temperature bounds.


Parameter Applicable Symbol MDS Default Units
Name Components
VSPOLY/1 Salts, CI solids C1i x — MOLE-VOLUME
TEMPERATURE
VSPOLY/2, ..., 5 Salts, CI solids C2i, ..., C5i x 0 MOLE-VOLUME
TEMPERATURE
VSPOLY/6 Salts, CI solids C6i x 0 MOLE-VOLUME
TEMPERATURE
VSPOLY/7 Salts, CI solids C7i x 1000 MOLE-VOLUME
TEMPERATURE

IK-CAPE Equation
The IK-CAPE equation is:

Linear extrapolation of Vi*,s versus T occurs outside of temperature bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VSPO/1 C1i — X — — MOLE-
VOLUME
VSPO/2, ..., 10 C2i, ..., C10i 0 X — — MOLE-
VOLUME
TEMPERATURE
VSPO/11 C11i 0 X — — TEMPERATURE
VSPO/12 C12i 1000 X — — TEMPERATURE

174 2 Thermodynamic Property Models


DIPPR
The DIPPR equation is:

Linear extrapolation of ρi*,s versus T occurs outside of temperature bounds.


Vi*,s = 1 / ρi*,s
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
The model returns solid molar volume for pure components.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DNSDIP/1 C1i — x — — MOLE-
DENSITY
DNSDIP/2, ..., 5 C2i, ..., C5i 0 x — — MOLE-
DENSITY,
TEMPERATURE
DNSDIP/6 C6i 0 x — — TEMPERATURE
DNSDIP/7 C7i 1000 x — — TEMPERATURE

NIST ThermoML Polynomial

Linear extrapolation of ρi*,s versus T occurs outside of temperature bounds.


Vi*,s = 1 / ρi*,s
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DNSTMLPO/1 C1i — x — — MOLE-
DENSITY
DNSTMLPO/2,...,8 C2i, ..., C8i 0 x — — MOLE-
DENSITY,
TEMPERATURE
DNSTMLPO/9 nTerms 8 x — — —
DNSTMLPO/10 Tlower 0 x — — TEMPERATURE
DNSTMLPO/11 Tupper 1000 x — — TEMPERATURE

Liquid Volume Quadratic Mixing Rule


With i and j being components, the liquid volume quadratic mixing rule is:

2 Thermodynamic Property Models 175


Option Codes
Option Code Value Descriptions
1 0 Use normal pure component liquid volume model for all
components (default)
1 Use steam tables for water
2 0 Use mole basis composition (default)
1 Use mass basis composition

Parameter
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VLQKIJ Kij - x - - —

This model is not part of any property method. To use it, you will need to
define a property method on the Properties | Property Methods form.
Specify the route VLMXQUAD for VLMX on the Routes sheet of this form, or
the model VL2QUAD for VLMX on the Models sheet.

Heat Capacity Models


The Aspen Physical Property System has five built-in heat capacity models.
This section describes the heat capacity models available.
Model Type
Aqueous Infinite Dilution Heat Capacity Electrolyte liquid
Polynomial
Criss-Cobble Aqueous Infinite Dilution Electrolyte liquid
Ionic Heat Capacity
DIPPR/PPDS/IK-CAPE Liquid Heat Capacity Liquid
Aspen/DIPPR/Barin/PPDS/IK-CAPE Ideal Ideal gas
Gas Heat Capacity
Aspen/DIPPR/Barin/IK-CAPE Solid Heat Solid
Capacity

Aqueous Infinite Dilution Heat Capacity


The aqueous phase infinite dilution enthalpies, entropies, and Gibbs energies
are calculated from the heat capacity polynomial. The values are used in the
calculation of aqueous and mixed solvent properties of electrolyte solutions:

versus T is linearly extrapolated using the slope at C7i for T < C7i

versus T is linearly extrapolated using the slope at C8i for T < C8i

176 2 Thermodynamic Property Models


Parameter Applicable Symbol Default Units
Name/Element Components
CPAQ0/1 Ions, molecular solutes C1i — TEMPERATURE and
HEAT CAPACITY
CPAQ0/2,…,6 Ions, molecular solutes C2i, ..., C6i 0 TEMPERATURE and
HEAT CAPACITY
CPAQ0/7 Ions, molecular solutes C7i 0 TEMPERATURE
CPAQ0/8 Ions, molecular solutes C8i 1000 TEMPERATURE

If any of C4i through C6i is non-zero, absolute temperature units are


assumed for C1i through C6i . Otherwise, user input units for temperature are
used. The temperature limits are always interpreted in user input units.

Criss-Cobble Aqueous Infinite Dilution Ionic


Heat Capacity
The Criss-Cobble correlation for aqueous infinite dilution ionic heat capacity is
used if no parameters are available for the aqueous infinite dilution heat
capacity polynomial. From the calculated heat capacity, the thermodynamic
properties entropy, enthalpy and Gibbs energy at infinte dilution in water are
derived:

Parameter Applicable Symbol Default Units


Name Components
IONTYP Ions Ion Type 0 —
SO25C Anions MOLE-ENTROPY

Cations MOLE-ENTROPY

DIPPR/PPDS/IK-CAPE Liquid Heat Capacity


The Aspen Physical Property System has several submodels for calculating
liquid heat capacity. It uses parameter THRSWT/6 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/6 is This equation is used And this parameter is used
100 DIPPR CPLDIP
200 Barin CPLXP1, CPLXP2
301 PPDS CPLPDS
401 IK-CAPE heat capacity CPLPO
polynomial
403 IK-CAPE liquid heat CPLIKC
capacity

2 Thermodynamic Property Models 177


If THRSWT/6 is This equation is used And this parameter is used
503 NIST ThermoML CPLTMLPO
polynomial
506 NIST TDE equation CPLTDECS

The DIPPR/PPDS/IK-CAPE liquid heat capacity model is used to calculate pure


component liquid heat capacity and pure component liquid enthalpy. To use
this model, two conditions must exist:
• One of the parameters for calculating heat capacity (see table below) is
available.
• The component is not supercritical (HENRY-COMP).
The model uses a specific method (see Methods in Property Calculation
Methods and Routes):

Where
= Reference enthalpy calculated at Tref

= Ideal gas enthalpy

= Vapor enthalpy departure

= Enthalpy of vaporization

Tref is the reference temperature; it defaults to 298.15 K. You can enter a


different value for the reference temperature. This is useful when you want to
use this model for very light components or for components that are solids at
298.15K.
Activate this model by specifying the route DHL09 for the property DHL on
the Properties Property Methods Routes sheet. For equation of state property
method, you must also modify the route for the property DHLMX to use a
route with method 2 or 3, instead of method 1. For example, you can use the
route DHLMX00 or DHLMX30. You must ascertain that the route for DHLMX
that you select contains the appropriate vapor phase model and heat of
mixing calculations. Click the View button on the form to see details of the
route.
Optionally, you can specify that this model is used for only certain
components. The properties for the remaining components are then
calculated by the standard model. Use the parameter COMPHL to specify the
components for which this model is used. By default, all components with the
CPLDIP or CPLIKC parameters use this model.

178 2 Thermodynamic Property Models


DIPPR Liquid Heat Capacity
The DIPPR equation is used to calculate liquid heat capacity when parameter
THRSWT/6 is 100.
The DIPPR equation is:

Linear extrapolation occurs for Cp*,l versus T outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPLDIP/1 C1i — x — — MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPLDIP/2, ..., 5 C2i, ..., C5i 0 x — — MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPLDIP/6 C6i 0 x — — TEMPERATURE
CPLDIP/7 C7i 1000 x — — TEMPERATURE
TREFHL Tref 298.15 — — — TEMPERATURE
COMPHL — — — — — —

To specify that the model is used for a component, enter a value of 1.0 for
COMPHL.
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)

PPDS Liquid Heat Capacity


The PPDS equation is used to calculate liquid heat capacity when parameter
THRSWT/6 is 301.
The PPDS equation is:

Where R is the gas constant.


Linear extrapolation occurs for Cp*,l versus T outside of bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPLPDS/1 C1i — — — — —
CPLPDS/2 C2i 0 — — — —
CPLPDS/3 C3i 0 — — — —
CPLPDS/4 C4i 0 — — — —
CPLPDS/5 C5i 0 — — — —
CPLPDS/6 C6i 0 — — — —
CPLPDS/7 C7i 0 x — — TEMPERATURE

2 Thermodynamic Property Models 179


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPLPDS/8 C8i 1000 x — — TEMPERATURE

IK-CAPE Liquid Heat Capacity


Two IK-CAPE equations can be used to calculate liquid heat capacity. Linear
extrapolation occurs for Cp*,l versus T outside of bounds for either equation.
When THRSWT/6 is 403, the IK-CAPE liquid heat capacity equation is used.
The equation is:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
CPLIKC/1 C1i — x — — MOLE-HEAT-
T CAPACITY
CPLIKC/2,...,4 C2i, ..., C4i 0 x — — MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPLIKC/5 C5i 0 x — — MOLE-HEAT-
CAPACITY,
TEMPERATURE †
CPLIKC/6 C6i 0 x — — TEMPERATURE
CPLIKC/7 C7i 1000 x — — TEMPERATURE

† If C5i is non-zero, absolute temperature units are assumed for C2i through
C5i. Otherwise, user input units for temperature are used. The temperature
limits are always interpreted in user input units.
When THRSWT/6 is 401, the IK-CAPE heat capacity polynomial is used.The
equation is:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
CPLPO/1 C1i — X — — MOLE-CAPACITY
CPLPO/2,…,10 C2i, ..., C10i 0 X — — MOLE-CAPACITY
TEMPERATURE
CPLPO/11 C11i 0 X — — TEMPERATURE
CPLPO/12 C12i 1000 X — — TEMPERATURE

See Pure Component Temperature-Dependent Properties for details on the


THRSWT parameters.

180 2 Thermodynamic Property Models


NIST Liquid Heat Capacity
Two NIST equations can be used to calculate liquid heat capacity. Linear
extrapolation occurs for Cp*,l versus T outside of bounds for either equation.
When THRSWT/6 is 503, the ThermoML polynomial is used to calculate liquid
heat capacity:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
CPLTMLPO/1 C1i — X — — J/K^2/mol
CPLTMLPO/2,…,5 C2i, ..., C5i 0 X — — J/K^2/mol
CPLTMLPO/6 nTerms 5 X — — —
CPLTMLPO/7 Tlower 0 X — — TEMPERATURE
CPLTMLPO/8 Tupper 1000 X — — TEMPERATURE

When THRSWT/6 is 506, the TDE equation is used to calculate liquid heat
capacity:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
CPLTDECS/1 C1i — X — — MOLE-HEAT-
CAPACITY
CPLTDECS/2,…,4 C2i, ..., C4i 0 X — — MOLE-HEAT-
CAPACITY
CPLTDECS/5 B 0 X — — MOLE-HEAT-
CAPACITY
CPLTDECS/6 Tci — X — — TEMPERATURE
CPLTDECS/7 nTerms 4 X — — —
CPLTDECS/8 Tlower 0 X — — TEMPERATURE
CPLTDECS/9 Tupper 1000 X — — TEMPERATURE

See Pure Component Temperature-Dependent Properties for details on the


THRSWT parameters.

Aspen/DIPPR/Barin/PPDS/IK-CAPE Ideal
Gas Heat Capacity
The Aspen Physical Property System has several submodels for calculating
ideal gas heat capacity. It uses parameter THRSWT/7 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.

2 Thermodynamic Property Models 181


If THRSWT/7 is This equation is used And this parameter is
used
0 Ideal gas heat capacity CPIG
polynomial
107 DIPPR CPIGDP
200 Barin CPIXP1, CPIXP2, CPIXP3
301 PPDS CPIGDS
401 IK-CAPE heat capacity CPIGPO
polynomial
503 NIST ThermoML CPITMLPO
polynomial
513 NIST Aly-Lee CPIALEE

These equations are also used to calculate ideal gas enthalpies, entropies,
and Gibbs energies.

Aspen Ideal Gas Heat Capacity Polynomial


The ideal gas heat capacity polynomial is available for components stored in
ASPENPCD, AQUEOUS, and SOLIDS databanks. This model is also used in
PCES.

Cp*,ig is linearly extrapolated using slope at


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
CPIG/1 C1i — — — — MOLE-HEAT-CAPACITY,
TEMPERATURE
CPIG/2, ..., 6 C2i, ..., C6i 0 — — — MOLE-HEAT-CAPACITY,
TEMPERATURE
CPIG/7 C7i 0 — — — TEMPERATURE
CPIG/8 C8i 1000 — — — TEMPERATURE
CPIG/9, 10, C9i, C10i, C11i — — — — MOLE-HEAT-CAPACITY,
11 TEMPERATURE †

† If C10i or C11i is non-zero, then absolute temperature units are assumed for
C9i through C11i. Otherwise, user input temperature units are used for all
parameters. User input temperature units are always used for C1i through C8i.

NIST ThermoML Polynomial


This equation can be used when parameter CPITMLPO is available.

182 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
CPITMLPO /1 C1i — x — — J/K^2/mol
CPITMLPO /2, C2i, ..., C6i 0 x — — J/K^2/mol
..., 6
CPITMLPO/7 nTerms 6 x — — —
CPITMLPO /8 Tlower 0 x — — TEMPERATURE
CPITMLPO /9 Tupper 1000 x — — TEMPERATURE

DIPPR
The DIPPR ideal gas heat capacity equation by Aly and Lee 1981 is:

No extrapolation is used with this equation.


(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPIGDP/1 C1i — x — — MOLE-HEAT-
CAPACITY
CPIGDP/2 C2i 0 x — — MOLE-HEAT-
CAPACITY
CPIGDP/3 C3i 0 x — — TEMPERATURE ††
CPIGDP/4 C4i 0 x — — MOLE-HEAT-
CAPACITY
CPIGDP/5 C5i 0 x — — TEMPERATURE ††
CPIGDP/6 C6i 0 x — — TEMPERATURE
CPIGDP/7 C7i 1000 x — — TEMPERATURE

†† Absolute temperature units are assumed for C3i and C5i. The temperature
limits are always interpreted in user input units.

NIST Aly-Lee
This equation is the same as the DIPPR Aly and Lee equation above, but it
uses a different parameter set. Note that elements 6 and 7 of the CPIALEE
parameter are not used in the equation.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPIALEE/1 C1i — x — — MOLE-HEAT-
CAPACITY
CPIALEE/2 C2i 0 x — — MOLE-HEAT-
CAPACITY
CPIALEE/3 C3i 0 x — — TEMPERATURE ††
CPIALEE/4 C4i 0 x — — MOLE-HEAT-
CAPACITY

2 Thermodynamic Property Models 183


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPIALEE/5 C5i 0 x — — TEMPERATURE ††
CPIALEE/8 C6i 0 x — — TEMPERATURE
CPIALEE/9 C7i 1000 x — — TEMPERATURE

†† Absolute temperature units are assumed for C3i and C5i. The temperature
limits are always interpreted in user input units.

PPDS
The PPDS equation is:

where R is the gas constant.


Linear extrapolation of Cp*,ig versus T is performed outside temperature
bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPIGDS/1 C1i — — — — TEMPERATURE
CPIGDS/2, …, 8 C2i, ..., C8i 0 — — — —
CPIGDS/9 C9i 0 — — — TEMPERATURE
CPIGDS/10 C10i 1000 — — — TEMPERATURE

IK-CAPE Heat Capacity Polynomial


The equation is:

Linear extrapolation of Cp*,ig versus T is performed outside temperature


bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPIGPO/1 C1i — X — — MOLE-CAPACITY
CPIGPO/2,…,10 C2i, ..., C10i 0 X — — MOLE-CAPACITY
TEMPERATURE
CPIGPO/11 C11i 0 X — — TEMPERATURE
CPIGPO/12 C12i 1000 X — — TEMPERATURE

184 2 Thermodynamic Property Models


References
Data for the Ideal Gas Heat Capacity Polynomial: Reid, Prausnitz and Poling,
The Properties of Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1987).
The Aspen Physical Property System combustion data bank, JANAF
Thermochemical Data, Compiled and calculated by the Thermal Research
Laboratory of Dow Chemical Company.
F. A. Aly and L. L. Lee, "Self-Consistent Equations for Calculating the Ideal
Gas Heat Capacity, Enthalpy, and Entropy, Fluid Phase Eq., Vol. 6, (1981), p.
169.

Aspen/DIPPR/Barin/IK-CAPE Solid Heat


Capacity
The Aspen Physical Property System has several submodels for calculating
solid heat capacity. It uses parameter THRSWT/5 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If THRSWT/5 is This equation is used And this parameter is
used
0 Aspen solid heat capacity CPSPO1
polynomial
100 DIPPR CPSDIP
200 Barin CPSXP1, CPSXP2, …,
CPSXP7
401 IK-CAPE heat capacity CPSPO
polynomial
503 NIST ThermoML CPSTMLPO
polynomial

The enthalpy, entropy, and Gibbs energy of solids are also calculated from
these equations:

Aspen Solid Heat Capacity Polynomial


The Aspen equation is:

Linear extrapolation occurs for Cp,i*,s versus T outside of bounds.


Parameter Applicable Symbol MDS Default Units
Name Components
CPSPO1/1 Solids, Salts C1i x — †
CPSPO1/2, ..., 6 Solids, Salts C2i, ..., C6i x 0 †
CPSPO1/7 Solids, Salts C7i x 0 †
CPSPO1/8 Solids, Salts C8i x 1000 †

† The units are TEMPERATURE and HEAT-CAPACITY for all elements. If any of
C4i through C6i are non-zero, absolute temperature units are assumed for

2 Thermodynamic Property Models 185


elements C1i through C6i. Otherwise, user input temperature units are
assumed for all elements. The temperature limits are always interpreted in
user input units.

DIPPR
The DIPPR equation is:

Linear extrapolation occurs for Cp,i*,s versus T outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPSDIP/1 C1i — x — — MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPSDIP/2,...,5 C2i, ..., C5i 0 x — — MOLE-HEAT-
CAPACITY,
TEMPERATURE
CPSDIP/6 C6i 0 x — — TEMPERATURE
CPSDIP/7 C7i 1000 x — — TEMPERATURE

(Other DIPPR equations may sometimes be used. See Pure Component


Temperature-Dependent Properties for details.)

NIST ThermoML Polynomial


The equation is:

Linear extrapolation occurs for Cp,i*,s versus T outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPSTMLPO/1 C1i — x — — J/K^2/mol
CPSTMLPO/2,...,5C2i, ..., C5i 0 x — — J/K^2/mol
CPSTMLPO/6 nTerms 5 x — — —
CPSTMLPO/7 Tlower 0 x — — TEMPERATURE
CPSTMLPO/8 Tupper 1000 x — — TEMPERATURE

IK-CAPE Heat Capacity Polynomial


The equation is:

Linear extrapolation occurs for Cp,i*,s versus T outside of bounds.

186 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
CPSPO/1 C1i — X — — MOLE-CAPACITY
CPSPO/2,…,10 C10i 0 X — — MOLE-CAPACITY
TEMPERATURE
CPSPO/11 C11i 0 X — — TEMPERATURE
CPSPO/12 C12i 1000 X — — TEMPERATURE

Solubility Correlations
The Aspen Physical Property System has three built-in solubility correlation
models. This section describes the solubility correlation models available.
Model Type
Henry's constant Gas solubility in liquid
Water solubility Water solubility in organic liquid
Hydrocarbon solubility Hydrocarbon solubility in water-rich
liquid

Henry's Constant
The Henry's constant model is used when Henry's Law is applied to calculate
K-values for dissolved gas components in a mixture. Henry's Law is available
in all activity coefficient property methods, such as the WILSON property
method. The model calculates Henry's constant for a dissolved gas component
(i) in one or more solvents (A or B):

Where:
wA =

ln HiA(T, pA*,l) =

Linear extrapolation occurs for ln HiA versus T outside of bounds.

HiA(T, P) =

The parameter is obtained from the Brelvi-O'Connell model. pA*,l is


obtained from the Antoine model. is obtained from the appropriate activity
coefficient model.

2 Thermodynamic Property Models 187


The Henry's constants aiA, biA, ciA, diA, and eiA are specific to a solute-solvent
pair. They can be obtained from regression of gas solubility data. The Aspen
Physical Property System has a large number of built-in Henry's constants for
many solutes in solvents. These parameters were obtained using data from
the Dortmund Databank. See Physical Property Data, Chapter 1, for details.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VC VcA — — 0.001 3.5 MOLE-VOLUME
HENRY/1 aiA †† x — — PRESSURE,
TEMPERATURE †
HENRY/2 biA 0 x — — TEMPERATURE †
HENRY/3 ciA 0 x — — TEMPERATURE †
HENRY/4 diA 0 x — — TEMPERATURE †
HENRY/5 TL 0 x — — TEMPERATURE
HENRY/6 TH 2000 x — — TEMPERATURE
HENRY/7 eiA 0 x — — TEMPERATURE †

† If any of biA, ciA, and eiA are non-zero, absolute temperature units are
assumed for all coefficients. If biA, ciA, and eiA are all zero, the others are
interpreted in input units. The temperature limits are always interpreted in
input units.

†† If aiA is missing, is set to zero and the weighting factor wA is


renormalized.

Water Solubility
This model calculates solubility of water in a hydrocarbon-rich liquid phase.
The model is used automatically when you model a hydrocarbon-water
system with the free-water option. See Free-Water Immiscibility Simplification
in Free-Water and Three-Phase Calculations for details.
The expression for the liquid mole fraction of water in the ith hydrocarbon
species is:

No extrapolation is used with this equation.


The parameters for about 60 components are stored in the Aspen Physical
Property System pure component databank.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
WATSOL/1 C1i fcn(Tbi, SGi, Mi) — -10.0 33.0 —
WATSOL/2 C2i fcn(Tbi, SGi, Mi) — -10000.0 3000.0 TEMPERATURE †
WATSOL/3 C3i 0 — -0.05 0.05 TEMPERATURE †

188 2 Thermodynamic Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
WATSOL/4 C4i 0 — 0.0 500 TEMPERATURE †
WATSOL/5 C5i 1000 — 4.0 1000 TEMPERATURE †

† Absolute temperature units are assumed for elements 2 through 5.

Hydrocarbon Solubility
This model calculates solubility of hydrocarbon in a water-rich liquid phase.
The model is used automatically when you model a hydrocarbon-water
system with the dirty-water option. See Free-Water Immiscibility
Simplification in Free-Water and Rigorous Three-Phase Calculations for
details.
The expression for the liquid mole fraction of the ith hydrocarbon species in
water is:

No extrapolation is used with this equation.


The parameters for about 40 components are stored in the Aspen Physical
Property System pure component databank.
Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
HCSOL/1 C1i fcn(carbon — -1000.0 1000.0 —
number) †
HCSOL/2 C2i 0 — -100000.0 100000.0 TEMPERATURE ††
HCSOL/3 C3i 0 — -100.0 100.0 TEMPERATURE ††
HCSOL/4 C4i 0 — 0.0 500 TEMPERATURE
HCSOL/5 C5i 1000 — 4.0 1000 TEMPERATURE

† For Hydrocarbons and pseudocomponents, the default values are estimated


by the method given by API Procedure 9A2.17 at 25 C.
†† Absolute temperature units are assumed for elements 2 and 3. The
temperature limits are always interpreted in user input units.

Reference
C. Tsonopoulos, Fluid Phase Equilibria, 186 (2001), 185-206.

2 Thermodynamic Property Models 189


Other Thermodynamic Property
Models
The Aspen Physical Property System has some built-in additional
thermodynamic property models that do not fit in any other category. This
section describes these models:
• Cavett Liquid Enthalpy Departure
• Barin Equations for Gibbs Energy, Enthalpy, Entropy and Heat Capacity
• Electrolyte NRTL Enthalpy
• Electrolyte NRTL Gibbs Energy
• Liquid Enthalpy from Liquid Heat Capacity Correlation
• Enthalpies Based on Different Reference States
• Helgeson Equations of State
• Quadratic Mixing Rule

Cavett
The general form for the Cavett model is:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TC Tci — — 5.0 2000.0 TEMPERATURE
PC pci — — 105 108 PRESSURE
DHLCVT ZC X 0.1 0.5 —

Barin Equations for Gibbs Energy, Enthalpy,


Entropy, and Heat Capacity
The following equations are used when parameters from the Aspen Physical
Property System inorganic databank are retrieved.
• Gibbs energy:
(1)

• Enthalpy:
(2)

• Entropy:
(3)

190 2 Thermodynamic Property Models


• Heat capacity:
(4)

α refers to an arbitrary phase which can be solid, liquid, or ideal gas. For each
phase, multiple sets of parameters from 1 to n are present to cover multiple
temperature ranges. The value of the parameter n depends on the phase.
(See tables that follow.) When the temperature is outside all these
temperature ranges, linear extrapolation of properties versus T is performed
using the slope at the end of the nearest temperature bound.
The four properties Cp, H, S, and G are interrelated as a result of the
thermodynamic relationships:

There are analytical relationships between the expressions describing the


properties Cp, H, S, and G (equations 1 to 4). The parameters an,i to hn,i can
occur in more than one equation.
The Aspen Physical Property System has other models which can be used to
calculate temperature-dependent properties which the BARIN equations can
calculate. The Aspen Physical Property System uses the parameters in
THRSWT to determine which model is used. See Pure Component
Temperature-Dependent Properties for details.
If this parameter is 200 Then the BARIN equations are
used to calculate
THRSWT/3 Liquid vapor pressure
THRSWT/5 Solid heat capacity
THRSWT/6 Liquid heat capacity
THRSWT/7 Ideal gas heat capacity

Solid Phase
The parameters in range n are valid for temperature: Tn,ls < T < Tn,hs
When you specify this parameter, be sure to specify at least elements 1
through 3.
Parameter Name † Symbol Default MDS Lower Upper Units
/Element Limit Limit
CPSXPn/1 Tn,ls — x — — TEMPERATURE
CPSXPn/2 Tn,hs — x — — TEMPERATURE
CPSXPn/3 an,is — x — — ††
CPSXPn/4 bn,is 0 x — — ††
CPSXPn/5 cn,is 0 x — — ††
CPSXPn/6 dn,is 0 x — — ††

2 Thermodynamic Property Models 191


Parameter Name † Symbol Default MDS Lower Upper Units
/Element Limit Limit
CPSXPn/7 en,is 0 x — — ††
CPSXPn/8 fn,is 0 x — — ††
CPSXPn/9 gn,is 0 x — — ††
CPSXPn/10 hn,is 0 x — — ††

† n is 1 through 7. CPSXP1 vector stores solid parameters for the first


temperature range. CPSXP2 vector stores solid parameters for the second
temperature range, and so on.
†† TEMPERATURE, ENTHALPY, ENTROPY

Liquid Phase
The parameters in range n are valid for temperature: Tn,ll < T < Tn,hl
When you specify this parameter, be sure to specify at least elements 1
through 3.
Parameter Name † Symbol Default MDS Lower Upper Units
/Element Limit Limit
CPLXPn/1 Tn,ll — x — — TEMPERATURE
CPLXPn/2 Tn,hl — x — — TEMPERATURE
l
CPLXPn/3 an,i — x — — ††
CPLXPn/4 bn,il 0 x — — ††
CPLXPn/5 cn,il 0 x — — ††
CPLXPn/6 dn,il 0 x — — ††
l
CPLXPn/7 en,i 0 x — — ††
CPLXPn/8 fn,il 0 x — — ††
l
CPLXPn/9 gn,i 0 x — — ††
CPLXPn/10 hn,il 0 x — — ††

† n is 1 through 2. CPLXP1 stores liquid parameters for the first temperature


range. CPLXP2 stores liquid parameters for the second temperature range.
†† TEMPERATURE, ENTHALPY, ENTROPY

Ideal Gas Phase


The parameters in range n are valid for temperature: Tn,lig < T < Tn,hig
When you specify this parameter, be sure to specify at least elements 1
through 3.
Parameter Name † Symbol Default MDS Lower Upper Units
/Element Limit Limit
CPIXPn/1 Tn,lig — x — — TEMPERATURE
CPIXPn/2 Tn,hig — x — — TEMPERATURE
ig
CPIXPn/3 an,i — x — — ††
CPIXPn/4 bn,iig 0 x — — ††
CPIXPn/5 cn,iig 0 x — — ††
CPIXPn/6 dn,iig 0 x — — ††
ig
CPIXPn/7 en,i 0 x — — ††

192 2 Thermodynamic Property Models


Parameter Name † Symbol Default MDS Lower Upper Units
/Element Limit Limit
CPIXPn/8 fn,iig 0 x — — ††
ig
CPIXPn/9 gn,i 0 x — — ††
CPIXPn/10 hn,iig 0 x — — ††

† n is 1 through 3. CPIXP1 vector stores ideal gas parameters for the first
temperature range. CPIXP2 vector stores ideal gas parameters for the second
temperature range, and so on.
†† TEMPERATURE, ENTHALPY, ENTROPY

Electrolyte NRTL Enthalpy


The equation for the electrolyte NRTL enthalpy model is:

The molar enthalpy Hm* and the molar excess enthalpy Hm*E are defined with
the asymmetrical reference state: the pure solvent water and infinite dilution
of molecular solutes and ions. (here * refers to the asymmetrical reference
state.)
Hw* is the pure water molar enthalpy, calculated from the Ideal Gas model
and the ASME Steam Table equation-of-state. (here * refers to pure
component.)

Hs*,l is the enthalpy contribution from a non-water solvent. It is calculated as


usual for components in activity coefficient models:

Hs*,l(T) = Hs*,ig + DHVs(T,p) - ΔHs,vap(T).


The term DHVs(T,p) = Hs*,v - Hs*,ig is the vapor enthalpy departure
contribution to liquid enthalpy; option code 5 determines how this is
calculated.

The property Hk is calculated from the infinite dilution aqueous phase heat
capacity polynomial model, by default. If polynomial model parameters are
not available, it is calculated from the Criss-Cobble model for ions and from
Henry's law for molecular solutes.
The subscript k can refer to a molecular solute defined as a Henry's
component (i), or a cation (c), or an anion (a):

Hm*E is excess enthalpy and is calculated from the electrolyte NRTL activity
coefficient model.
See Criss-Cobble model and Henry's law model for more information.

2 Thermodynamic Property Models 193


Option codes can improve the performance of this model when using mixed
solvents and Henry components. See Option Codes for Enthalpy Models for
details.
Parameter Applicable Symbol Default Units
Name Components
IONTYP Ions † Ion 0 —
SO25C Cations ∞,aq — MOLE-ENTROPY
Sc (T=298)
Anions ∞,aq — MOLE-ENTROPY
Sa (T=298)
DHAQFM Ions, Molecular Solutes Δf Hk∞,aq — MOLE-ENTHALPY
††
CPAQ0 Ions, Molecular Solutes ∞,aq — HEAT-CAPACITY
Cp,k
††
DHFORM Molecular Solutes †† Δf Hi*,ig — MOLE-ENTHALPY

Water, Solvents Δf Hw*,ig — MOLE-ENTHALPY

CPIG Molecular Solutes Cp,i*,ig — †††


*,ig
Water, Solvents Cp,w — †††

† IONTYP is not needed if CPAQ0 is given for ions.


†† DHFORM is not used if DHAQFM and CPAQ0 are given for molecular solutes
(components declared as Henry's components). If CPAQ0 is missing, DHFORM
and Henry's constants are used to calculate infinite dilution enthalpy for
solutes.
††† The unit keywords for CPIG are TEMPERATURE and HEAT-CAPACITY. If
CPIG/10 or CPIG/11 is non-zero, then absolute temperature units are
assumed for CPIG/9 through CPIG/11. Otherwise, user input temperature
units are used for all elements of CPIG. User input temperature units are
always used for other elements of CPIG.

Electrolyte NRTL Gibbs Free Energy


The equation for the NRTL Gibbs free energy model is:

The molar Gibbs free energy and the molar excess Gibbs free energy Gm* and
Gm*E are defined with the asymmetrical reference state: as pure water and
infinite dilution of molecular solutes and ions. (* refers to the asymmetrical
reference state.) The ideal mixing term is calculated normally, where j refers
to any component. The molar Gibbs free energy of pure water (or
thermodynamic potential) μw* is calculated from the ideal gas contribution.
This is a function of the ideal gas heat capacity and the departure function.
(here * refers to the pure component.)

The departure function is obtained from the ASME steam tables.

194 2 Thermodynamic Property Models


μs*,l is the Gibbs free energy contribution from a non-water solvent. It is
calculated as usual for components in activity coefficient models.

The aqueous infinite dilution thermodynamic potential μk is calculated from
the infinite dilution aqueous phase heat capacity polynomial model, by
default. Subscript k refers to any ion or molecular solute. If polynomial model
parameters are not available, it is calculated from the Criss-Cobble model for
ionic solutes:

∞ ∞
Because Δf Hk ,aq and Δf Gk ,aq are based on a molality scale, and μk∞ is based
on mole fraction scale, the term RT ln(1000/Mw) is added.

For molecular solutes, μk∞ is calculated from Henry's law:

G*E is calculated from the electrolyte NRTL activity coefficient model.


See the Criss-Cobble model and Henry's law model for more information.
Option codes can improve the performance of this model when using mixed
solvents and Henry components. See Option Codes for Gibbs Energy Models
for details.
Parameter Applicable Symbol Default Units
Name Components
IONTYP Ions † Ion 0 —
SO25C Cations † ∞,aq — MOLE-ENTROPY
Sc (T=298)
Anions † ∞,aq — MOLE-ENTROPY
Sa (T=298)
DGAQFM Ions, Molecular Solutes Δf Gk∞,aq — MOLE-ENTHALPY
††
CPAQ0 Ions, Molecular Solutes ∞,aq — HEAT-CAPACITY
Cp,k
††
DGFORM Molecular Solutes †† Δf Gi — MOLE-ENTHALPY

Water, Solvents Δf Gw — MOLE-ENTHALPY

CPIG Molecular Solutes Cp,i*,ig — †††


*,ig
Water, Solvents Cp,w — †††

† IONTYP and SO25C are not needed if CPAQ0 is given for ions.
†† DGFORM is not needed if DHAQFM and CPAQ0 are given for molecular
solutes.

2 Thermodynamic Property Models 195


††† The unit keywords for CPIG are TEMPERATURE and HEAT-CAPACITY. If
CPIG/10 or CPIG/11 is non-zero, then absolute temperature units are
assumed for CPIG/9 through CPIG/11. Otherwise, user input temperature
units are used for all elements of CPIG. User input temperature units are
always used for other elements of CPIG.

Liquid Enthalpy from Liquid Heat Capacity


Correlation
Liquid enthalpy is directly calculated by integration of liquid heat capacity:

The reference enthalpy is calculated at Tref as:

Where:
Hi*,ig = Ideal gas enthalpy
Hi*,v - Hi*,ig = Vapor enthalpy departure from equation of state

ΔvapHi*,l = Heat of vaporization from Watson/DIPPR/IK-CAPE model

Tref = Reference temperature, specified by user. Defaults to


298.15 K
See DIPPR/IK-CAPE Liquid Heat Capacity for parameter requirement and
additional details.

Enthalpies Based on Different Reference


States
Two property methods, WILS-LR and WILS-GLR, are available to calculate
enthalpies based on different reference states. The WILS-LR property method
is based on saturated liquid reference state for all components. The WILS-GLR
property method allows both ideal gas and saturated liquid reference states
for different components.
These property methods use an enthalpy method that optimizes the accuracy
tradeoff between liquid heat capacity, heat of vaporization, and vapor heat
capacity at actual process conditions. This highly recommended method
eliminates many of the problems associated with accurate thermal properties
for both phases, especially the liquid phase.
The liquid enthalpy of mixture is calculated by the following equation (see the
table labeled Liquid Enthalpy Methods):

Where:

196 2 Thermodynamic Property Models


Hmig = Enthalpy of ideal gas mixture
=

Hi*,ig = Ideal gas enthalpy of pure component i


(Hml-Hmig) = Enthalpy departure of mixture
For supercritical components, declared as Henry's components, the enthalpy
departure is calculated as follows:

For subcritical components:


Hml-Hmig =

HmE,l =

HA*,l-HA*,ig = Enthalpy departure of pure component A


H*,ig and H*,l can be calculated based on either saturated liquid or ideal gas as
reference state as described in the sections that follow.
For the WILS-LR property method, H*,ig and H*,l are calculated based on the
saturated liquid reference state for all components.
For the WILS-GLR property method, H*,ig and H*,l can be calculated based on
the saturated liquid reference state for some components and the ideal gas
reference state for other components. You can set the value of a pure
component parameter called RSTATE to specify the reference state for each
component. RSTATE = 1 denotes ideal gas reference state. RSTATE = 2
denotes saturated liquid reference state. If it is not set, the following default
rules apply based on the normal boiling point of the component, i, TB(i):
• If TB(i) <= 298.15 K, ideal gas reference state is used
• If TB(i) > 298.15 K, saturated liquid reference state is used.

Saturated Liquid as Reference State


The saturated liquid enthalpy at temperature T is calculated as follows:

Where:
Hiref,l = Reference enthalpy for liquid state at Tiref,l
Cp,i*,l = Liquid heat capacity of component i
The saturated liquid Gibbs free energy is calculated as follows:

2 Thermodynamic Property Models 197


Where:
Giref,l = Reference Gibbs free energy for liquid state at Tiref,l

φi*,l = Liquid fugacity coefficient of component i

p = System pressure
ref
p = Reference pressure (=101325 N/m2)
For the WILS-LR property method, Hiref,l and Giref,l default to zero (0). The
reference temperature Tiref,l defaults to 273.15K.
For the WILS-GLR property method, the reference temperature Tiref,l defaults
to 298.15K and Hiref,l defaults to:

And Giref,l defaults to:

Where:
Hiref,ig = Ideal gas enthalpy of formation for liquid state at
298.15K
Giref,ig = Ideal gas Gibbs free energy of formation for liquid
state at 298.15K

ΔHi*,v = Vapor enthalpy departure of component i

ΔGi*,v = Vapor Gibbs free energy departure of component i

ΔvapHi* = Enthalpy of vaporization of component i

Note that we cannot default the liquid reference enthalpy and Gibbs free
energy to zero, as is the case for WILS-LR, because it will cause inconsistency
with the enthalpy of components that use ideal-gas reference state. The
default values used result in the enthalpies of all components being on the
same basis. In fact, if you enter values for Hiref,l and Giref,l for a liquid-
reference state component you must make sure that they are consistent with
each other and are consistent with the enthalpy basis of the remaining
components in the mixture. If you enter a value for Hiref,l, you should also
enter a value for Giref,l to ensure consistency.
When the liquid-reference state is used, the ideal gas enthalpy at
temperature T is not calculated from the integration of the ideal gas heat
capacity equation (see Ideal Gas as Reference State section below). For
consistency, it is calculated from liquid enthalpy as follows:

Where:

198 2 Thermodynamic Property Models


Ticon,l = Temperature of conversion from liquid to vapor
enthalpy for component i

ΔvapHi*(Ticon,l) = Heat of vaporization of component i at


temperature of Tcon,l

ΔHi*,v(Ticon,l, pi*,l) = Vapor enthalpy departure of component i at the


conversion temperature and vapor pressure pi*,l
pi*,l = Liquid vapor pressure of component i
= Ideal gas heat capacity of component i

Ticon,l is the temperature at which one crosses from liquid state to the vapor
state. This is a user defined temperature that defaults to the system
temperature T. Ticon,l may be selected such that heat of vaporization for
component i at the temperature is most accurate.
The vapor enthalpy is calculated from ideal gas enthalpy as follows:

Where:

ΔHi*,v(T, P) = Vapor enthalpy departure of pure component i at the


system temperature and pressure
The liquid heat capacity and the ideal gas heat capacity can be calculated
from the ASPEN, DIPPR, IK-CAPE, BARIN, NIST/TDE, or other available
models. The heat of vaporization can be calculated from the Watson, DIPPR,
IK-CAPE, NIST/TDE, or other available models. The enthalpy departure is
obtained from an equation-of-state that is being used in the property method.
For WILS-LR and WILS-GLR, the ideal gas equation of state is used.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
RSTATE † — 2 — — — —
TREFHL Tiref,l †† — — — TEMPERATURE
DHLFRM Hiref,l ††† — — — MOLE ENTHALPY
DGLFRM Giref,l †††† — — — MOLE ENTHALPY
TCONHL Ticon,l T — — — TEMPERATURE

† Enthalpy reference state given by RSTATE. 2 denotes saturated liquid as


reference state.
†† For WILS-LR property method TREFHL defaults to 273.15K. For WILS-GLR
property method, TREFHL defaults to 298.15 K.
††† For WILS-LR property method, DHLFRM defaults to zero (0). For WILS-
GLR property method, DHLFRM defaults to the equation above.
†††† For WILS-LR property method, DGLFRM defaults to zero (0). For WILS-
GLR property method, DGLFRM defaults to the equation above.
Liquid heat capacity equation is required for all components.

2 Thermodynamic Property Models 199


Ideal Gas as Reference State
The saturated liquid enthalpy is calculated as follows:

Where:
Hiref,ig = Reference state enthalpy for ideal gas at Tiref,ig
= Heat of formation of ideal gas at 298.15 K by default
Tiref,ig = Reference temperature corresponding to Hiref,ig.
Defaults to 298.15 K
Ticon,ig = The temperature at which one crosses from vapor
state to liquid state. This is a user defined
temperature that defaults to the system temperature
T. Ticon,igmay be selected such that heat of
vaporization of component i at the temperature is
most accurate.
The ideal gas enthalpy is calculated as follows:

The vapor enthalpy is calculated as follows:

The liquid heat capacity and the ideal gas heat capacity can be calculated
from the ASPEN, DIPPR, IK-CAPE, BARIN, NIST/TDE, or other available
models. The heat of vaporization can be calculated from the Watson, DIPPR,
IK-CAPE, NIST/TDE, or other available models. The enthalpy departure is
obtained from an equation of state that is being used in the property method.
For WILS-LR and WILS-GLR, the ideal gas equation of state is used.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
RSTATE — 1† — — — —
TREFHI Tiref,ig †† — — — TEMPERATURE
DHFORM Hiref,ig — — — — MOLE ENTHALPY
TCONHI Ticon,ig T — — — TEMPERATURE

† Enthalpy reference state RSTATE for a component. Value of 1 denotes ideal


gas.

††For components with TB ≤ 298.15 K, RSTATE defaults to 1 (ideal gas).


TREFHI defaults to 298.15 K. For components with TB > 298.15 K, RSTATE
defaults to 2 (liquid) and TREFHI does not apply to these components. See
the Saturated Liquid as Reference State section for more details.

200 2 Thermodynamic Property Models


Helgeson Equations of State
The Helgeson equations of state for standard volume , heat capacity ,
entropy , enthalpy of formation , and Gibbs energy of formation
at infinite dilution in aqueous phase are:

Where:

2 Thermodynamic Property Models 201


Where:

Ψ = Pressure constant for a solvent (2600 bar for water)

θ = Temperature constant for a solvent (228 K for


water)

ω = Born coefficient

ε = Dielectric constant of a solvent

Tr = Reference temperature (298.15 K)


Pr = Reference pressure (1 bar)

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
AHGPAR/1, ... , a1, ..., a4 0 — — — —
4
CHGPAR/1, ... , c1, c2 x — — — —
2
DHAQHG 0 — -0.5x1010 0.5x1010 MOLE-ENTHALPY

DGAQHG 0 — -0.5x1010 0.5x1010 MOLE-ENTHALPY

S25HG 0 — -0.5x1010 0.5x1010 MOLE-ENTROPY

OMEGHG 0 — -0.5x1010 0.5x1010 MOLE-ENTHALPY

If pressure is under 200 bar, AHGPAR may not be required.

References
Tanger, J.C. IV and H.C. Helgeson, "Calculation of the thermodynamic and
transport properties of aqueous species at high pressures and temperatures:
Revised equation of state for the standard partial properties of ions and
electrolytes," American Journal of Science, Vol. 288, (1988), p. 19-98.
Shock, E.L. and H.C. Helgeson, "Calculation of the thermodynamic and
transport properties of aqueous species at high pressures and temperatures:

202 2 Thermodynamic Property Models


Correlation algorithms for ionic species and equation of state predictions to 5
kb and 1000 °C," Geochimica et Cosmochimica Acta, Vol. 52, p. 2009-2036.
Shock, E.L., H.C. Helgeson, and D.A. Sverjensky, "Calculation of the
thermodynamic and transport properties of aqueous species at high pressures
and temperatures: Standard partial molal properties of inorganic neutral
species," Geochimica et Cosmochimica Acta, Vol. 53, p. 2157-2183.

Quadratic Mixing Rule


The quadratic mixing rule is a general-purpose mixing rule which can be
applied to various properties. For a given property Q, with i and j being
components, the rule is:

The pure component properties Qi and Qj are calculated by the default model
for that property, unless modified by option codes. Composition xi and xj is in
mole fraction unless modified by option codes. Kij is a binary parameter
specific to the mixing rule for each property. A variation on the equation using
the logarithm of the property is used for viscosity.

2 Thermodynamic Property Models 203


3 Transport Property Models

This section describes the transport property models available in the Aspen
Physical Property System. The following table provides an overview of the
available models. This table lists the Aspen Physical Property System model
names, and their possible use in different phase types, for pure components
and mixtures.

Transport Property Models


Viscosity models Model name Phase(s) Pure Mixture
Andrade Liquid Mixture MUL2ANDR L — X
Viscosity
Andrade/DIPPR/PPDS/IK-CAPE MUL0ANDR L X —
API Liquid Viscosity MUL2API L — X
API 1997 Liquid Viscosity MULAPI97 L — X
Aspen Liquid Mixture Viscosity MUASPEN L — X
ASTM Liquid Mixture Viscosity MUL2ASTM L — X
Chapman-Enskog-Brokaw MUV0CEB V X —
/DIPPR/PPDS/IK-CAPE
Chapman-Enskog-Brokaw- MUV2BROK, V — X
Wilke Mixing Rule MUV2WILK
Chung-Lee-Starling Low MUV0CLSL, V X X
Pressure MUV2CLSL
Chung-Lee-Starling MUV0CLS2, VL X X
MUV2CLS2,
MUL0CLS2,
MUL2CLS2
Dean-Stiel Pressure Correction MUV0DSPC, V X X
MUV2DSPC
IAPS Viscosity MUV0H2O V X —
MUL0H2O L X —
Jones-Dole Electrolyte MUL2JONS L — X
Correction
Letsou-Stiel MUL0LEST, L X X
MUL2LEST
Lucas MUV0LUC, V X X
MUV2LUC

204 3 Transport Property Models


Viscosity models Model name Phase(s) Pure Mixture
TRAPP viscosity MUL0TRAP, VL X X
MUL2TRAP,
MUV0TRAP,
MUV2TRAP
Twu liquid viscosity MUL2TWU L — X
Viscosity quadratic mixing rule MUL2QUAD L — X

Thermal conductivity Model name Phase(s) Pure Mixture


models
Chung-Lee-Starling Thermal KV0CLS2, VL X X
Conductivtity KV2CLS2,
KL0CLS2,
KL2CLS2
IAPS Thermal Conductivity for KV0H2O V X —
Water KL0H2O L X —
Li Mixing Rule KL2LI L X X
Riedel Electrolyte Correction KL2RDL L — X
Sato-Riedel/DIPPR/PPDS/ IK- KL0SR, L X X
CAPE KL2SRVR
Stiel-Thodos/DIPPR/PPDS/ IK- KV0STLP V X —
CAPE
Stiel-Thodos Pressure KV0STPC, V X X
Correction KV2STPC
TRAPP Thermal Conductivity KV0TRAP, VL X X
KV2TRAP,
KL0TRAP,
KL2TRAP
Vredeveld Mixing Rule KL2SRVR L X X
Wassiljewa-Mason-Saxena KV2WMSM V X X
mixing rule

Diffusivity models Model name Phase(s) Pure Mixture


Chapman-Enskog-Wilke-Lee DV0CEWL V — X
Binary
Chapman-Enskog-Wilke-Lee DV1CEWL V — X
Mixture
Dawson-Khoury-Kobayashi DV1DKK V — X
Binary
Dawson-Khoury-Kobayashi DV1DKK V — X
Mixture
Nernst-Hartley Electrolytes DL0NST, L — X
DL1NST
Wilke-Chang Binary DL0WC2 L — X
Wilke-Chang Mixture DL1WC L — X

Surface tension models Model name Phase(s) Pure Mixture


Liquid Mixture Surface Tension SIG2IDL L — X
API Surface Tension SIG2API L — X

3 Transport Property Models 205


Surface tension models Model name Phase(s) Pure Mixture
Hakim-Steinberg-Stiel/DIPPR SIG0HSS, L X —
/IK-CAPE SIG2HSS
IAPS surface tension SIG0H2O L X —
Onsager-Samaras Electrolyte SIG2ONSG L — X
Correction
Modified MacLeod-Sugden SIG2MS L — X

Viscosity Models
The Aspen Physical Property System has the following built-in viscosity
models:
Model Type
Andrade Liquid Mixture Viscosity Liquid
Andrade/DIPPR/PPDS/IK-CAPE Pure component liquid
API liquid viscosity Liquid
API 1997 liquid viscosity Liquid
Chapman-Enskog-Brokaw/DIPPR/IK-CAPE Low pressure vapor,
pure components
Chapman-Enskog-Brokaw-Wilke Mixing Rule Low pressure vapor,
mixture
Chung-Lee-Starling Low Pressure Low pressure vapor
Chung-Lee-Starling Liquid or vapor
Dean-Stiel Pressure correction Vapor
IAPS viscosity Water or steam
Jones-Dole Electrolyte Correction Electrolyte
Letsou-Stiel High temperature liquid
Lucas Vapor
TRAPP viscosity Vapor or liquid
Aspen Liquid Mixture Viscosity Liquid
ASTM Liquid Mixture Viscosity Liquid
Twu liquid viscosity Liquid
Viscosity quadratic mixing rule Liquid

Andrade Liquid Mixture Viscosity


The liquid mixture viscosity is calculated by the modified Andrade equation:

Where:
kij =

206 3 Transport Property Models


mij =

fi depends on the option code for the model MUL2ANDR.


If first option code of Then fi is
MUL2ANDR is
0 (Default) Mole fraction of component i
1 Mass fraction of component i

Note that the Andrade liquid mixture viscosity model is called from other
models. The first option codes of these models cause fi to be mole or mass
fraction when Andrade is used in the respective models. To maintain
consistency across models, if you set the first option code for MUL2ANDR to
1, you should also the set the first option code of the other models to 1, if
they are used in your simulation.
Model Model Name
MUL2JONS Jones-Dole Electrolyte Viscosity model
DL0WCA Wilke-Chang Diffusivity model (binary)
DL1WCA Wilke-Chang Diffusivity model (mixture)
DL0NST Nernst-Hartley Electrolyte Diffusivity model (binary)
DL1NST Nernst-Hartley Electrolyte Diffusivity model (mixture)

The binary parameters kij and mij allow accurate representation of complex
liquid mixture viscosity. Both binary parameters default to zero.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
ANDKIJ/1 aij 0 — — — —
ANDKIJ/2 bij 0 — — — —
ANDMIJ/1 cij 0 — — — —
ANDMIJ/2 dij 0 — — — —

The pure component liquid viscosity ηi*,l can be calculated by these


equations:
• Andrade
• DIPPR
• IK-CAPE
See the Andrade/DIPPR/IK-CAPE Pure Component Liquid Viscosity model for
descriptions.

Andrade/DIPPR/PPDS/IK-CAPE Pure
Component Liquid Viscosity
The Aspen Physical Property System has several submodels for calculating
pure component liquid viscosity. It uses parameter TRNSWT/1 to determine
which submodel is used. See Pure Component Temperature-Dependent
Properties for details.
If TRNSWT/1 is This equation is used And this parameter is used
0 Andrade MULAND

3 Transport Property Models 207


If TRNSWT/1 is This equation is used And this parameter is used
101 DIPPR MULDIP
301 PPDS MULPDS
401 IK-CAPE polynomial equation MULPO
404 IK-CAPE exponential equation MULIKC
508 NIST TDE equation MULNVE
509 NIST PPDS9 MULPPDS9

Andrade Liquid Viscosity


The Andrade equation is:

Linear extrapolation of ln(viscosity) versus 1/T occurs for temperatures


outside bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULAND/1 Ai — X — — VISCOSITY,
TEMPERATURE †
MULAND/2 Bi — X — — TEMPERATURE †
MULAND/3 Ci — X — — TEMPERATURE †
MULAND/4 Tl 0.0 X — — TEMPERATURE
MULAND/5 Th 500.0 X — — TEMPERATURE

† If Bi or Ci is non-zero, absolute temperature units are assumed for Ai, Bi,


and Ci. Otherwise, all coefficients are interpreted in user input temperature
units. The temperature limits are always interpreted in user input units.

DIPPR Liquid Viscosity


The equation for the DIPPR liquid viscosity model is:

Linear extrapolation of ln(viscosity) versus 1/T occurs for temperatures


outside bounds.
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULDIP/1 C1i — X — — VISCOSITY,
TEMPERATURE ††
MULDIP/2, ..., 5 C2i, ..., C5i 0 X — — TEMPERATURE ††
MULDIP/6 C6i 0 X — — TEMPERATURE
MULDIP/7 C7i 1000 X — — TEMPERATURE

†† If any of C3i through C5i are non-zero, absolute temperature units are
assumed for C3i through C5i. Otherwise, all coefficients are interpreted in user
input temperature units. The temperature limits are always interpreted in
user input units.

208 3 Transport Property Models


PPDS
The PPDS equation is:

Linear extrapolation of viscosity versus T occurs for temperatures outside


bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULPDS/1 C1i — — — — —
MULPDS/2 C2i — — — —
MULPDS/3 C3i — — — TEMPERATURE
MULPDS/4 C4i — — — TEMPERATURE
MULPDS/5 C5i — — — — VISCOSITY
MULPDS/6 C6i — — — TEMPERATURE
MULPDS/7 C7i — — — TEMPERATURE

NIST PPDS9 Equation


This is the same as the PPDS equation above, but it uses parameter
MULPPDS9. Note that the parameters are in a different order.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULPPDS9/1 C5i — — — — Pa*S
MULPPDS9/2 C1i — — — —
MULPPDS9/3 C2i — — — TEMPERATURE
MULPPDS9/4 C3i — — — TEMPERATURE
MULPPDS9/5 C4i — — — — TEMPERATURE
MULPPDS9/6 C6i — — — TEMPERATURE
MULPPDS9/7 C7i — — — TEMPERATURE

IK-CAPE Liquid Viscosity Model


The IK-CAPE liquid viscosity model includes both exponential and polynomial
equations.

Exponential

Linear extrapolation of viscosity versus T occurs for temperatures outside


bounds.
Parameter SymbolDefault MDS Lower Upper Units
Name/Element Limit Limit
MULIKC/1 C1i — X — — VISCOSITY

3 Transport Property Models 209


Parameter SymbolDefault MDS Lower Upper Units
Name/Element Limit Limit
MULIKC/2 C2i 0 X — — TEMPERATURE †††
MULIKC/3 C3i 0 X — — VISCOSITY
MULIKC/4 C4i 0 X — — TEMPERATURE
MULIKC/5 C5i 1000 X — — TEMPERATURE

††† Absolute temperature units are assumed for C2i. The temperature limits
are always interpreted in user input units.

Polynomial

Linear extrapolation of viscosity versus T occurs for temperatures outside


bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULPO/1 C1i — X — — VISCOSITY
MULPO/2, ..., 10 C2i, ..., C10i 0 X — — VISCOSITY,
TEMPERATURE
MULPO/11 C11i 0 X — — TEMPERATURE
MULPO/12 C12i 1000 X — — TEMPERATURE

NIST TDE Equation

Linear extrapolation of viscosity versus T occurs for temperatures outside


bounds.
Absolute temperature units are assumed for C2i, C3i, and C4i. The temperature
limits are always interpreted in user input units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULNVE/1 C1i — X — — —
MULNVE/2, 3, 4 C2i, C3i, C4i 0 X — — TEMPERATURE
MULNVE/5 C5i 0 X — — TEMPERATURE
MULNVE/6 C6i 1000 X — — TEMPERATURE

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 439.

210 3 Transport Property Models


API Liquid Viscosity
The liquid mixture viscosity is calculated using a combination of the API and
Andrade/DIPPR equations. This model is recommended for petroleum and
petrochemical applications. It is used in the CHAO-SEA, GRAYSON, LK-PLOCK,
PENG-ROB, and RK-SOAVE option sets.
For pseudocomponents, the API model is used:

Where:
fcn = A correlation based on API Procedures and Figures 11A4.1, 11A4.2,
and 11A4.3 (API Technical Data Book, Petroleum Refining, 4th
edition)
Vml is obtained from the API liquid volume model.
For real components, the Andrade/DIPPR model is used.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TB Tbi — — 4.0 2000.0 TEMPERATURE
API APIi — — -60.0 500.0 —

API 1997 Liquid Viscosity


The liquid mixture viscosity is calculated using a combination of the API and
Andrade/DIPPR equations. This model is recommended over the earlier API
viscosity model.
This model is applicable to petroleum fractions with normal boiling points from
150 F to 1200 F and API gravities between 0 and 75. Testing by AspenTech
indicates that this model is slightly more accurate than the Twu model for
light and medium boiling petroleum components, while the Twu model is
superior for heavy fractions.
For pseudocomponents, the API model is used:

Where:
fcn = A correlation based on API Procedures and Figures 11A4.2, 11A4.3,
and 11A4.4 (API Technical Data Book, Petroleum Refining, 1997
edition)
Vml is obtained from the API liquid volume model.
For real components, the Andrade/DIPPR model is used.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TB Tbi — — 4.0 2000.0 TEMPERATURE
API APIi — — -60.0 500.0 —

3 Transport Property Models 211


Aspen Liquid Mixture Viscosity
The liquid mixture viscosity is calculated by the equation:

Where:
Xi = Mole fraction or weight fraction of component i
kij = Symmetric binary parameter (kij = kji)
lij = Antisymmetric binary parameter (lij = -lji)

The pure component liquid viscosity ηi*,l can be calculated by these


equations:
• Andrade
• DIPPR
• IK-CAPE
See the Andrade/DIPPR/IK-CAPE Pure Component Liquid Viscosity model for
descriptions.
The binary parameters kij and lij allow accurate representation of complex
liquid mixture viscosity. Both binary parameters default to zero.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MUKIJ kij 0 — -100.0 100.0 —
MULIJ lij 0 — 100.0 100.0 —

ASTM Liquid Mixture Viscosity


It is generally difficult to predict the viscosity of a mixture of viscous
components. For hydrocarbons, the following weighting method (ASTM †) is
known to give satisfactory results:

Where:
wi = Weight fraction of component i

μm = Absolute viscosity of the mixture (N-sec/sqm)

μi = Viscosity of component i (N-sec/sqm)

log = Common logarithm (base 10)


f = An adjustable parameter, typically in the
range of 0.5 to 1.0

212 3 Transport Property Models


The individual component viscosities are calculated by the Andrade, DIPPR, or
IK-CAPE equation. The parameter f can be specified by setting the value for
MULOGF for the first component in the component list (as defined on the
Components | Specifications | Selection sheet).
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MULOGF f 1.0 — 0.0 2.0 —

† "Petroleum Refining, 1 Crude Oil, Petroleum Products, Process Flowsheets",


Institut Francais du Petrole Publications, 1995, p. 130.

Chapman-Enskog-
Brokaw/DIPPR/PPDS/IK-CAPE Vapor
Viscosity
The Aspen Physical Property System has several submodels for calculating
pure component low pressure vapor viscosity. It uses parameter TRNSWT/2
to determine which submodel is used. See Pure Component Temperature-
Dependent Properties for details.
If TRNSWT/2 is This equation is used And this parameter is
used
0 Chapman-Enskog- —
Brokaw
102 DIPPR MUVDIP
301 PPDS MUVPDS
302 PPDS kinetic theory MUVCEB
401 IK-CAPE polynomial MUVPO
equation
402 IK-CAPE Sutherland MUVSUT
equation
503 NIST ThermoML MUVTMLPO
polynomial

Chapman-Enskog-Brokaw
The equation for the Chapman-Enskog model is:

Where:

Ωη =

A parameter δ is used to determine whether to use the Stockmayer or


Lennard-Jones potential parameters for ε/k (energy parameter) and σ
(collision diameter). To calculate δ, the dipole moment p and either the
Stockmayer parameters or Tb and Vb are needed. The polarity correction is
from Brokaw.

3 Transport Property Models 213


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —
-24
MUP pi — — 0.0 5x10 DIPOLEMOMENT
STKPAR/1 (εi/k) ST fcn(Tbi, Vbi, pi) — X — TEMPERATURE

STKPAR/2 σiST fcn(Tbi, Vbi, pi) X — — LENGTH

LJPAR/1 (εi/k)LJ fcn(Tci, ωi) X — — TEMPERATURE

LJPAR/2 σiLJ fcn(Tci, pci, ωi) X — — LENGTH

DIPPR Vapor Viscosity


The equation for the DIPPR vapor viscosity model is:

When necessary, the vapor viscosity is extrapolated beyond this temperature


range linearly with respect to T, using the slope at the temperature limits.
(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
PCES uses the DIPPR equation in estimating vapor viscosity.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MUVDIP/1 C1i — X — — VISCOSITY
MUVDIP/2 C2i 0 X — — —
MUVDIP/3, 4 C3i, C4i 0 X — — TEMPERATURE †
MUVDIP/5 †† 0 X — — —
MUVDIP/6 C6i 0 X — — TEMPERATURE
MUVDIP/7 C7i 1000 X — — TEMPERATURE

† If any of C2i through C4i are non-zero, absolute temperature units are
assumed for C1i through C4i. Otherwise, all coefficients are interpreted in user
input temperature units. The temperature limits are always interpreted in
user input units.
†† MUVDIP/5 is not used in this equation. It is normally set to zero. The
parameter is provided for consistency with other DIPPR equations.

PPDS
The PPDS submodel includes both the basic PPDS vapor viscosity equation
and the PPDS kinetic theory vapor viscosity equation. For either equation,
linear extrapolation of viscosity versus T occurs for temperatures outside
bounds.

PPDS Vapor Viscosity


The equation is:

214 3 Transport Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MUVPDS/1 C1i — — — — VISCOSITY
MUVPDS/2 C2i 0 — — — —
MUVPDS/3 C3i 0 — — — —
MUVPDS/4 C4i 0 — — — TEMPERATURE
MUVPDS/5 C5i 1000 — — — TEMPERATURE

PPDS Kinetic Theory Vapor Viscosity


The equation is:

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —
MUVCEB/1 C1i — — — — LENGTH
MUVCEB/2 C2i — — — — TEMPERATURE †
MUVCEB/3 C3i 0 — — — —
MUVCEB/4 C4i 0 — — — TEMPERATURE
MUVCEB/5 C5i 1000 — — — TEMPERATURE

† Absolute temperature units are assumed for C2i . The temperature limits are
always interpreted in user input units.

IK-CAPE Vapor Viscosity


The IK-CAPE vapor viscosity model includes both the Sutherland equation and
the polynomial equation. For either equation, linear extrapolation of viscosity
versus T occurs for temperatures outside bounds.

Sutherland Equation

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
MUVSUT/1 C1i — X — — VISCOSITY
MUVSUT/2 C2i 0 X — — TEMPERATURE ††
MUVSUT/3 C3i 0 X — — TEMPERATURE

3 Transport Property Models 215


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MUVSUT/4 C4i 1000 X — — TEMPERATURE

†† If C2i is non-zero, absolute temperature units are assumed for C1i and C2i.
Otherwise, all coefficients are interpreted in user input temperature units. The
temperature limits are always interpreted in user input units.

Polynomial

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
MUVPO/1 C1i — X — — VISCOSITY
MUVPO/2, ..., 10 C2i, ..., C10i 0 X — — VISCOSITY,
TEMPERATURE
MUVPO/11 C11i 0 X — — TEMPERATURE
MUVPO/12 C12i 1000 X — — TEMPERATURE

NIST ThermoML Polynomial

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
MUVTMLPO/1 C1i — X — — Pa*s/T
MUVTMLPO/2, ..., 4 C2i , ..., C4i 0 X — — Pa*s/T
MUVTMLPO/5 nTerms 4 X — — —
MUVTMLPO/6 Tlower 0 X — — TEMPERATURE
MUVTMLPO/7 Tupper 1000 X — — TEMPERATURE

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling. The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 392.

Chapman-Enskog-Brokaw-Wilke Mixing
Rule
The low pressure vapor mixture viscosity is calculated by the Wilke
approximation of the Chapman-Enskog equation:

216 3 Transport Property Models


For Φij,the formulation by Brokaw is used:

Where:

The Stockmayer or Lennard-Jones potential parameters ε/k (energy


parameter) and σ (collision diameter) and the dipole moment p are used to
calculate δ. The k represents Boltzmann's constant 1.38065 x 10-23 J/K. If the
Stockmayer parameters are not available, δ is estimated from Tb and Vb:

Where p is in debye.

The pure component vapor viscosity ηi*,v (p = 0) can be calculated using the
Chapman- Enskog-Brokaw/DIPPR (or another) low pressure vapor viscosity
model.

Ensure that you supply parameters for ηi*,v (p = 0).


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
MW Mi — — 1.0 5000.0 —
-24
MUP pi — — 0.0 5x10 DIPOLEMOMENT

3 Transport Property Models 217


Parameter Symbol Default MDS Lower Upper Units
Name/ Limit Limit
Element
STKPAR/1 (εi/k)ST fcn(Tbi, Vbi, pi) — X — TEMPERATURE

STKPAR/2 σiST fcn(Tbi, Vbi, pi) X — — LENGTH

References
R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of Gases and
Liquids, 3rd ed., (New York: McGraw-Hill, 1977), pp. 410–416.

Chung-Lee-Starling Low-Pressure Vapor


Viscosity
The low-pressure vapor viscosity by Chung, Lee, and Starling is:

Where the viscosity collision integral is:

The shape and polarity correction is:

The parameter pr is the reduced dipolemoment:

C1 is a constant of correlation.

The polar parameter κ is tabulated for certain alcohols and carboxylic acids.
The previous equations can be used for mixtures when applying these mixing
rules:

218 3 Transport Property Models


Where:
Vcij =

ξij = 0 (in almost all cases)

Tcij =

ζij = 0 (in almost all cases)

ωij =

Mij =

κij =

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCCLS Tci TC x 5.0 2000.0 TEMPERATURE
VCCLS Vci VC x 0.001 3.5 MOLE-VOLUME
MW Mi — — 1.0 5000.0 —
-24
MUP pi — — 0.0 5x10 DIPOLEMOMENT
OMGCLS ωi OMEGA x -0.5 2.0 —

CLSK κi 0.0 x 0.0 0.5 —

CLSKV ξij 0.0 x -0.5 -0.5 —

CLSKT ζij 0.0 x -0.5 0.5 —

The model specific parameters also affect the Chung-Lee-Starling Viscosity


and the Chung-Lee-Starling Thermal Conductivity models.

3 Transport Property Models 219


References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 396, p. 413.

Chung-Lee-Starling Viscosity
The Chung-Lee-Starling viscosity equation for vapor and liquid, high and low
pressure is:

With:
f1 =

f2 =

FC =

The molar density can be calculated using an equation-of-state model (for


example, the Benedict-Webb-Rubin). The parameter pr is the reduced
dipolemoment:

C1 and C2 are constants of correlation.

The polar parameter κ is tabulated for certain alcohols and carboxylic acids.
For low pressures, f1 is reduced to 1.0 and f2 becomes negligible. The
equation reduces to the low pressure vapor viscosity model by Chung-Lee and
Starling.
The previous equations can be used for mixtures when applying these mixing
rules:

220 3 Transport Property Models


Where:
Vcij =

ξij = 0 (in almost all cases)

Tcij =

ζij = 0 (in almost all cases)

ωij =

Mij =

κij =

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TCCLS Tci TC x 5.0 2000.0 TEMPERATURE
VCCLS Vci VC x 0.001 3.5 MOLE-VOLUME
MW Mi — — 1.0 5000.0 —
-24
MUP pi — — 0.0 5x10 DIPOLEMOMENT
OMGCLS ωi OMEGA x -0.5 2.0 —

CLSK κi 0.0 x 0.0 0.5 —

CLSKV ξij 0.0 x -0.5 -0.5 —

CLSKT ζij 0.0 x -0.5 0.5 —

The model specific parameters affect the results of the Chung-Lee-Starling


Thermal Conductivity and Low Pressure Viscosity models as well.

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 427.

3 Transport Property Models 221


Dean-Stiel Pressure Correction
The residual vapor viscosity or the pressure correction to low pressure vapor
viscosity by Dean and Stiel is:

Where ηv (p = 0) is obtained from a low pressure viscosity model (for


example, Chapman-Enskog-Brokaw). The dimensionless-making factor ξ is:
ξ =

Tc =

M =

pc =

Vcm =

Zcm =

ρrm = Vcm / Vmv

The parameter Vmv is obtained from Redlich-Kwong equation-of-state.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —
VC Vci — — 0.001 3.5 MOLE-VOLUME

IAPS Viscosity for Water


The IAPS viscosity models, developed by the International Association for
Properties of Steam, calculate vapor and liquid viscosity for water and steam.
These models are used in option sets STEAMNBS and STEAM-TA.
The general form of the equation for the IAPS viscosity models is:

ηw=fcn(T, p)
Where:
fcn = Correlation developed by IAPS
The models are only applicable to water. There are no parameters required
for the models.

222 3 Transport Property Models


Jones-Dole Electrolyte Correction
The Jones-Dole model calculates the correction to the liquid mixture viscosity
of a solvent mixture, due to the presence of electrolytes:

Where:

ηsolv = Viscosity of the liquid solvent mixture, by default


calculated by the Andrade/DIPPR model

Δηcal = Contribution to the viscosity correction due to


apparent electrolyte ca

The parameter ηsolv can be calculated by different models depending on


option code 3 for MUL2JONS:
Option Code Solvent liquid mixture viscosity
Value model
Andrade liquid mixture viscosity
0
model (default)
1 Viscosity quadratic mixing rule
2 Aspen liquid mixture viscosity
model

The parameter Δηcal can be calculated by three different equations.


If these parameters are available Use this equation

IONMOB and IONMUB Jones-Dole
IONMUB Breslau-Miller
— Carbonell

† When the concentration of apparent electrolyte exceeds 0.1 M, the Breslau-


Miller equation is used instead.

Jones-Dole
The Jones-Dole equation is:
(1)

Where:
= Concentration of apparent electrolyte ca (2)

xcaa = Mole fraction of apparent electrolyte ca (3)


Aca = (4)

La = (5)

3 Transport Property Models 223


Lc = (6)

Bca = (7)

When the electrolyte concentration exceeds 0.1 M, the Breslau-Miller equation


is used instead. This behavior can be disabled by setting the second option
code for MUL2JONS to 0.

Breslau-Miller
The Breslau-Miller equation is:
(8)

Where the effective volume Vc is given by:


(9)

for salts involving univalent ions


(9a)

for other salts

Carbonell
The Carbonell equation is:
(10)

Where:
Mk = Molecular weight of an apparent electrolyte
component k
You must provide parameters for the model used for the calculation of the
liquid mixture viscosity of the solvent mixture.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
CHARGE z 0.0 — — —
MW M — 1.0 5000.0 —
IONMOB/1 l1 — — — AREA, MOLES
IONMOB/2 l2 0.0 — — AREA, MOLES,
TEMPERATURE
IONMUB/1 b1 — — — MOLE-VOLUME
IONMUB/2 b2 0,0 — — MOLE-VOLUME,
TEMPERATURE

References
A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis
Horwood, 1985).

224 3 Transport Property Models


Letsou-Stiel
The Letsou-Stiel model calculates liquid viscosity at high temperatures for
0.76 ≤ Tr ≤ 0.98. This model is used in PCES.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
The general form for the model is:

ηlε = (ηlε)0 + ω(ηlε)1


Where:

(ηlε)0 =

(ηlε)1 =

ε =

ω =

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —
TC Tci — — 5.0 2000.0 TEMPERATURE
PC pci — — 105 108 PRESSURE
OMEGA ωi — — -0.5 2.0 —

References
R.C. Reid, J.M. Pransnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 471.

Lucas Vapor Viscosity


The equation for the Lucas vapor viscosity model is:

Where the dimensionless low pressure viscosity is given by:

The dimensionless-making group is:

3 Transport Property Models 225


The pressure correction factor Y is:

The polar and quantum correction factors at high and low pressure are:
FP =

FQ =

FPi (p = 0) =

FQi (p = 0) = fcn(Tri), but is only nonunity for the quantum


gates i = H2, D2, and He.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
The Lucas mixing rules are:
Tc =

pc =

M =

FP (p = 0) =

FQ (p = 0) =

Where A differs from unity only for certain mixtures.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
TCLUC Tci TC x 5.0 2000.0 TEMPERATURE
5 8
PCLUC pci PC x 10 10 PRESSURE
ZCLUC Zci ZC x 0.1 0.5 —
MW Mi — — 1.0 5000.0 —
-24
MUP pi — — 0.0 5x10 DIPOLEMOMENT

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 421, 431.

226 3 Transport Property Models


TRAPP Viscosity Model
The general form for the TRAPP viscosity model is:

Where:
The parameter is the mole fraction vector; fcn is a corresponding states
correlation based on the model for vapor and liquid viscosity TRAPP, by the
National Bureau of Standards (NBS, currently NIST) . The model can be used
for both pure components and mixtures. The model should be used for
nonpolar components only.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —
TCTRAP Tci TC x 5.0 2000.0 TEMPERATURE
5 8
PCTRAP pci PC x 10 10 PRESSURE
VCTRAP Vci VC x 0.001 3.5 MOLE-VOLUME
ZCTRAP Zci ZC x 0.1 1.0 —
OMGRAP ωi OMEGA x -0.5 3.0 —

References
J.F. Ely and H.J.M. Hanley, "Prediction of Transport Properties. 1. Viscosities
of Fluids and Mixtures," Ind. Eng. Chem. Fundam., Vol. 20, (1981), pp. 323–
332.

Twu Liquid Viscosity


The Twu liquid viscosity model is based upon the work of C.H. Twu (1985).
The correlation uses n-alkanes as a reference fluid and is capable of
predicting liquid viscosity for petroleum fractions with normal boiling points up
to 1340 F and API gravity up to -30.
Given the normal boiling point Tb and the specific gravity SG of the system to
be modeled, the Twu model estimates the viscosity of the n-alkane reference
fluid of the same normal boiling point at 100 F and 210 F, and its specific
gravity. These are used to estimates the viscosity of the system to be
modeled at 100 F and at 210 F, and these viscosities are used to estimate the
viscosity at the temperature of interest.

3 Transport Property Models 227


Where:
SG = Specific gravity of petroleum fraction
Tb = Normal boiling point of petroleum fraction, Rankine
SG° = Specific gravity of reference fluid with normal
boiling point Tb
T = Temperature of petroleum fraction, Rankine

η = Kinematic viscosity of petroleum fraction at T, cSt

ηi = Kinematic viscosity of petroleum fraction at 100 F


(i=1) and 210 F (i=2), cSt

η1°, η2° = Kinematic viscosity of reference fluid at 100 F and


210 F, cSt
Tc° = Critical temperature of reference fluid, Rankine

228 3 Transport Property Models


Reference
C.H. Twu, "Internally Consistent Correlation for Predicting Liquid Viscosities of
Petroleum Fractions," Ind. Eng. Chem. Process Des. Dev., Vol. 24 (1985), pp.
1287-1293

Viscosity Quadratic Mixing Rule


With i and j being components, the viscosity quadratic mixing rule is:

The pure component viscosity is calculated by the Andrade/DIPPR/PPDS/IK-


CAPE model.

Option Codes
Option Code Value Descriptions
1 0 Use mole basis composition (default)
1 Use mass basis composition

Parameter
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MLQKIJ Kij - x - - —

Thermal Conductivity Models


The Aspen Physical Property System has eight built-in thermal conductivity
models. This section describes the thermal conductivity models available.
Model Type
Chung-Lee-Starling Vapor or liquid
IAPS Water or steam
Li Mixing Rule Liquid mixture
Riedel Electrolyte Correction Electrolyte
Sato-Riedel/DIPPR/IK-CAPE Liquid
Solid Thermal Conductivity Polynomial Solid
Stiel-Thodos/DIPPR/IK-CAPE Low pressure vapor
Stiel-Thodos Pressure Correction Vapor
TRAPP Thermal Conductivity Vapor or liquid
Vredeveld Mixing Rule Liquid mixture
Wassiljewa-Mason-Saxena Mixing Rule Low pressure vapor

3 Transport Property Models 229


Chung-Lee-Starling Thermal Conductivity
The main equation for the Chung-Lee-Starling thermal conductivity model is:

Where:
f1 =

f2 =

Ψ =

η(p = 0) can be calculated by the low pressure Chung-Lee-Starling model. The


molar density can be calculated using an equation-of-state model (for
example, the Benedict-Webb-Rubin equation-of-state). The parameter pr is
the reduced dipolemoment:

The polar parameter κ is tabulated for certain alcohols and carboxylic acids.
For low pressures, f1 is reduced to 1.0 and f2 is reduced to zero. This gives
the Chung-Lee-Starling expression for thermal conductivity of low pressure
gases.

The same expressions are used for mixtures. The mixture expression for η (p
= 0) must be used. (See Chung-Lee-Starling Low-Pressure Vapor Viscosity.)

Where:

230 3 Transport Property Models


Vcij =

ξij = 0 (in almost all cases)

Tcij =

ζij = 0 (in almost all cases)

ωij =

Mij =

κij =

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TCCLS Tci TC x 5.0 2000.0 TEMPERATURE
VCCLS Vci VC x 0.001 3.5 MOLE-VOLUME
MW Mi — — 1.0 5000.0 —
-24
MUP pi — — 0.0 5x10 DIPOLEMOMENT
OMGCLS ωi OMEGA x -0.5 2.0 —

CLSK κi 0.0 x 0.0 0.5 —

CLSKV ξij 0.0 x -0.5 -0.5 —

CLSKT ζij 0.0 x -0.5 0.5 —

The model-specific parameters also affect the results of the Chung-Lee-


Starling Viscosity models.

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 505, 523.

IAPS Thermal Conductivity for Water


The IAPS thermal conductivity models were developed by the International
Association for Properties of Steam. These models can calculate vapor and
liquid thermal conductivity for water and steam. They are used in option sets
STEAMNBS and STEAM-TA.
The general form of the equation for the IAPS thermal conductivity models is:

λw=fcn(T, p)

3 Transport Property Models 231


Where:
fcn = Correlation developed by IAPS
The models are only applicable to water. No parameters are required.

Li Mixing Rule
Liquid mixture thermal conductivity is calculated using Li equation (Reid
et.al., 1987):

Where:

The pure component liquid molar volume Vi*,l is calculated from the Rackett
model.

The pure component liquid thermal conductivity λi*,l can be calculated by


three models:
• Sato Riedel
• DIPPR
• IK-CAPE
See the Sato Riedel/DIPPR/IK-CAPE model for descriptions.
Reference: R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases
and Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 550.

Riedel Electrolyte Correction


The Riedel model can calculate the correction to the liquid mixture thermal
conductivity of a solvent mixture, due to the presence of electrolytes:

Where:

λlsolv = Thermal conductivity of the liquid solvent mixture,


calculated by the Sato-Riedel model using the
Vredeveld mixing rule
xcaa = Mole fraction of the apparent electrolyte ca
ac, aa = Riedel ionic coefficient

232 3 Transport Property Models


Vml = Apparent molar volume computed by the Clarke
density model
Apparent electrolyte mole fractions are computed from the true ion mole-
fractions and ionic charge number. They can also be computed if you use the
apparent component approach. A more detailed discussion of this method is
found in Electrolyte Calculation.
You must provide parameters for the Sato-Riedel model. This model is used
for the calculation of the thermal conductivity of solvent mixtures.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
CHARGE z 0.0 — — —
IONRDL a 0.0 — — †

† THERMAL CONDUCTIVITY, MOLE-VOLUME


The behavior of this model can be changed using option codes (these codes
apply to the Vredeveld mixing rule).
Option Option Description
Code Value
1 0 Do not check ratio of KL max / KL min
1 Check ratio. If KL max / KL min > 2, set exponent to 1,
overriding option code 2.
2 0 Exponent is -2
1 Exponent is 0.4
2 Exponent is 1. This uses a weighted average of liquid thermal
conductivities.

Sato-Riedel/DIPPR/IK-CAPE Liquid
Thermal Conductivity
The Aspen Physical Property System has several submodels for calculating
pure component liquid thermal conductivity. It uses parameter TRNSWT/3 to
determine which submodel is used. See Pure Component Temperature-
Dependent Properties for details.
If TRNSWT/3 is This equation is used And this parameter is used
0 Sato-Riedel —
100 DIPPR KLDIP
301 PPDS KLPDS
401 IK-CAPE KLPO
503 NIST ThermoML KLTMLPO
polynomial
510 NIST PPDS8 equation KLPPDS8

Sato-Riedel
The Sato-Riedel equation is (Reid et al., 1987):

3 Transport Property Models 233


Where:
Tbri = Tbi / Tci
Tri = T / Tci

Note: Reduced temperature Tr is always calculated using absolute


temperature units.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —
TC Tci — — 5.0 2000.0 TEMPERATURE
TB Tbi — — 4.0 2000.0 TEMPERATURE

PPDS
The equation is:

Linear extrapolation of λ*,l versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KLPDS/1 C1i — — — — THERMAL-
CONDUCTIVITY
KLPDS/2 C2i 0 — — — —
KLPDS/3 C3i 0 — — — —
KLPDS/4 C4i 0 — — — —
KLPDS/5 C5i 0 — — — TEMPERATURE
KLPDS/6 C6i 1000 — — — TEMPERATURE

NIST PPDS8 Equation


The equation is

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
KLPPDS8/1 C1i — — — — THERMAL-
CONDUCTIVITY
KLPPDS8/2, ..., 7 C2i , ..., C7i 0 — — — —
KLPPDS8/8 TCi — — — — TEMPERATURE
KLPPDS8/9 nTerms 7 — — — —

234 3 Transport Property Models


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KLPPDS8/10 Tlower 0 — — — TEMPERATURE
KLPPDS8/11 Tupper 1000 — — — TEMPERATURE

DIPPR Liquid Thermal Conductivity


The DIPPR equation is:

Linear extrapolation of λ*,l versus T occurs outside of bounds.


(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
The DIPPR equation is used by PCES when estimating liquid thermal
conductivity.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KLDIP/1 C1i — x — — THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLDIP/2, ... , 5 C2i , ..., C5i 0 x — — THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLDIP/6 C6i 0 x — — TEMPERATURE
KLDIP/7 C7i 1000 x — — TEMPERATURE

NIST ThermoML Polynomial


The equation is:

Linear extrapolation of λ*,l versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KLTMLPO/1 C1i — x — — THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLTMLPO/2, ... , C2i , ..., C4i 0 x — — THERMAL-
4 CONDUCTIVITY,
TEMPERATURE
KLTMLPO/5 nTerms 4 x — — —
KLTMLPO/6 Tlower 0 x — — TEMPERATURE
KLTMLPO/7 Tupper 1000 x — — TEMPERATURE

IK-CAPE
The IK-CAPE equation is:

3 Transport Property Models 235


Linear extrapolation of λ*,l versus T occurs outside of bounds.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KLPO/1 C1i — x — — THERMAL-
CONDUCTIVITY
KLPO/2, ... , 10 C2i , ..., C10i 0 x — — THERMAL-
CONDUCTIVITY,
TEMPERATURE
KLPO/11 C11i 0 x — — TEMPERATURE
KLPO/12 C12i 1000 x — — TEMPERATURE

References
R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1977), p. 533.
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 550.

Solid Thermal Conductivity Polynomial


Thermal conductivity for solid pure components is calculated using the solid
thermal conductivity polynomial. For mixtures, the mole-fraction weighted
average is used.
For pure solids, thermal conductivity is calculated by:

For mixtures:

Linear extrapolation of λi*,s versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KSPOLY/1 a — — — — THERMAL
CONDUCTIVITY
KSPOLY/2, 3, 4, 5 b, c, d, e — — — — THERMAL
CONDUCTIVITY,
TEMPERATURE
KSPOLY/6 0 x — — TEMPERATURE

KSPOLY/7 1000 x — — TEMPERATURE

236 3 Transport Property Models


Stiel-Thodos/DIPPR/PPDS/IK-CAPE Vapor
Thermal Conductivity
The Aspen Physical Property System has several submodels for calculating
pure component low pressure vapor thermal conductivity. It uses parameter
TRNSWT/4 to determine which submodel is used. See Pure Component
Temperature-Dependent Properties for details.
If TRNSWT/4 is This equation is used And this parameter is
used
0 Stiel-Thodos —
102 DIPPR KVDIP
301 PPDS KVPDS
401 IK-CAPE KVPO
503 NIST ThermoML KVTMLPO
polynomial

Stiel-Thodos
The Stiel-Thodos equation is:

Where:

ηi*,v(p = 0) can be obtained from the Chapman-Enskog-Brokaw model.


Cpi*,ig is obtained from the Ideal Gas Heat Capacity model.
R is the universal gas constant.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —

DIPPR Vapor Thermal Conductivity


The DIPPR equation for vapor thermal conductivity is:

Linear extrapolation of λi*,v versus T occurs outside of bounds.


(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
The DIPPR equation is used in PCES when estimating vapor thermal
conductivity.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KVDIP/1 C1i — x — — THERMAL
CONDUCTIVITY
KVDIP/2 C2i 0 x — — —
KVDIP/3, 4 C3i, C4i 0 x — — TEMPERATURE †
KVDIP/5 — 0 x — — —

3 Transport Property Models 237


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KVDIP/6 C6i 0 x — — TEMPERATURE
KVDIP/7 C7i 1000 x — — TEMPERATURE

† If any of C2i through C4i are non-zero, absolute temperature units are
assumed for C1i through C4i. Otherwise, all coefficients are interpreted in user
input temperature units. The temperature limits are always interpreted in
user input units.

PPDS
The equation is:

Linear extrapolation of λi*,v versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KVPDS/1 C1i — — — — THERMAL-
CONDUCTIVITY
KVPDS/2 C2i 0 — — — THERMAL-
CONDUCTIVITY
KVPDS/3 C3i 0 — — — THERMAL-
CONDUCTIVITY
KVPDS/4 C4i 0 — — — THERMAL-
CONDUCTIVITY
KVPDS/5 C5i 0 — — — TEMPERATURE
KVPDS/6 C6i 1000 — — — TEMPERATURE

IK-CAPE Polynomial

Linear extrapolation of λi*,v versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KVPO/1 C1i — x — — THERMAL-
CONDUCTIVITY
KVPO/2, ... , 10 C2i, ..., C10i 0 x — — THERMAL-
CONDUCTIVITY,
TEMPERATURE
KVPO/11 C11i 0 x — — TEMPERATURE
KVPO/12 C12i 1000 x — — TEMPERATURE

238 3 Transport Property Models


NIST ThermoML Polynomial

Linear extrapolation of λi*,v versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
KVTMLPO/1 C1i — x — — THERMAL-
CONDUCTIVITY,
TEMPERATURE
KVTMLPO/2, ... , C2i, ..., C4i 0 x — — THERMAL-
4 CONDUCTIVITY,
TEMPERATURE
KVTMLPO/5 nTerms 4 x — — —
KVTMLPO/6 Tlower 0 x — — TEMPERATURE
KVTMLPO/7 Tupper 1000 x — — TEMPERATURE

References
R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquid,
4th ed., (New York: McGraw-Hill, 1987), p. 494.

Stiel-Thodos Pressure Correction Model


The pressure correction to a pure component or mixture thermal conductivity
at low pressure is given by:

Where:

ρrm =

The parameter Vmv can be obtained from Redlich-Kwong.

λv(p = 0) can be obtained from the low pressure Stiel-Thodos Thermal


Conductivity model (Stiel-Thodos/DIPPR).
This model should not be used for polar substances, hydrogen, or helium.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —
TC Tci — — 5.0 2000.0 TEMPERATURE
5 8
PC — — — 10 10 PRESSURE
VC Vci — — 0.001 3.5 MOLE-VOLUME
ZC Zci — — 0.1 0.5 —

3 Transport Property Models 239


References
R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquids,
4th ed., (New York: McGraw-Hill, 1987), p. 521.

Vredeveld Mixing Rule


Liquid mixture thermal conductivity is calculated using the Vredeveld equation
(Reid et al., 1977):

Where:
wi = Liquid phase weight fraction of component i

λi*,l = Pure component liquid thermal conductivity of component i

Where n is determined from two option codes on model KL2VR:


If option code 1 is Then n is determined by
0 (default) Option code 2, always
1
Option code 2, unless . In this case n is
set to 1.

If option code 2 is Then n is


0 (default) -2
1 0.4
2 1 (This uses a weighted average of liquid thermal
conductivities.)

For most systems, the ratio of maximum to minimum pure component liquid
thermal conductivity is between 1 and 2, where the exponent -2 is
recommended, and is the default value used.

Pure component liquid thermal conductivity λi*,l can be calculated by these


equations:
• Sato-Riedel
• DIPPR
• IK-CAPE
See the Sato-Riedel/DIPPR/IK-CAPE model for descriptions.
Reference: R.C. Reid, J.M. Prausnitz, and T.K. Sherwood, The Properties of
Gases and Liquids, 4th ed., (New York: McGraw-Hill, 1977), p. 533.

TRAPP Thermal Conductivity Model


The general form for the TRAPP thermal conductivity model is:

240 3 Transport Property Models


Where:
= Mole fraction vector
*,ig
Cpi = Ideal gas heat capacity calculated using the Aspen
Physical Property System or DIPPR ideal gas heat
capacity equations
fcn = Corresponding states correlation based on the
model for vapor and liquid thermal conductivity
made by the National Bureau of standards (NBS,
currently NIST)
The model can be used for both pure components and mixtures. The model
should be used for nonpolar components only.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —
TCTRAP Tci TC x 5.0 2000.0 TEMPERATURE
5 8
PCTRAP pci PC x 10 10 PRESSURE
VCTRAP Vci VC x 0.001 3.5 MOLE-VOLUME
ZCTRAP Zci ZC x 0.1 1.0 —
OMGRAP ωi OMEGA x -0.5 3.0 —

References
J.F. Ely and H.J. M. Hanley, "Prediction of Transport Properties. 2. Thermal
Conductivity of Pure Fluids and Mixtures," Ind. Eng. Chem. Fundam., Vol. 22,
(1983), pp. 90–97.

Wassiljewa-Mason-Saxena Mixing Rule


The vapor mixture thermal conductivity at low pressures is calculated from
the pure component values, using the Wassiljewa-Mason-Saxena equation:

Where:

λi*,v = Calculated by the Stiel-Thodos model or the DIPPR


thermal conductivity model (Stiel-Thodos/DIPPR)

ηi*,v(p = 0) = Obtained from the Chapman-Enskog-Brokaw


model

3 Transport Property Models 241


You must supply parameters for ηi*,v(p = 0) and λi*,v.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), pp. 530–531.

Diffusivity Models
The Aspen Physical Property System has seven built-in diffusivity models. This
section describes the diffusivity models available.
Model Type
Chapman-Enskog-Wilke-Lee (Binary) Low pressure vapor
Chapman-Enskog-Wilke-Lee (Mixture) Low pressure vapor
Dawson-Khoury-Kobayashi (Binary) Vapor
Dawson-Khoury-Kobayashi (Mixture) Vapor
Nernst-Hartley Electrolyte
Wilke-Chang (Binary) Liquid
Wilke-Chang (Mixture) Liquid

Chapman-Enskog-Wilke-Lee (Binary)
The binary diffusion coefficient at low pressures is calculated using
the Chapman-Enskog-Wilke-Lee model:

Where:

The collision integral for diffusion is:

ΩD =

The binary size and energy parameters are defined as:

σij =

242 3 Transport Property Models


εij =

A parameter δ is used to determine whether to use the Stockmayer or


Lennard-Jones potential parameters for ε/k (energy parameter ) and σ
(collision diameter). To calculate δ, the dipole moment p, and either the
Stockmayer parameters or Tb and Vb are needed.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
MW Mi — — 1.0 5000.0 —
-24
MUP pi — — 0.0 5x10 DIPOLEMOMENT
TB Tbi — — 4.0 2000.0 TEMPERATURE
VB Vb — — 0.001 3.5 MOLE-VOLUME
OMEGA ωi — — -0.5 2.0 —

STKPAR/1 (εi/k)ST fcn(Tbi, Vbi, pi) x — — TEMPERATURE

STKPAR/2 σiST fcn(Tbi, Vbi, pi) x — — LENGTH

LJPAR/1 (εi/k)LJ fcn(Tci, ωi) x — — TEMPERATURE

LJPAR/2 σiLJ fcn(Tci, pci, ωi) x — — LENGTH

References
R.C. Reid, J.M. Praunitz, and B.E. Poling, The Properties of Gases and Liquids,
4th ed., (New York: McGraw-Hill, 1987), p. 587.

Chapman-Enskog-Wilke-Lee (Mixture)
The diffusion coefficient of a gas into a gas mixture at low pressures is
calculated using an equation of Bird, Stewart, and Lightfoot by default (option
code 0):

If the first option code is set to 1, Blanc's law is used instead:

The binary diffusion coefficient Dijv(p = 0) at low pressures is calculated using


the Chapman-Enskog-Wilke-Lee model. (See Chapman-Enskog-Wilke-Lee
(Binary).)
You must provide parameters for this model.

3 Transport Property Models 243


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DVBLNC — 1 x — — —

DVBLNC is set to 1 for a diffusing component and 0 for a non-diffusing


component.

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 597.

Dawson-Khoury-Kobayashi (Binary)
The binary diffusion coefficient Dijv at high pressures is calculated from the
Dawson-Khoury-Kobayashi model:

Dijv(p = 0) is the low-pressure binary diffusion coefficient obtained from the


Chapman-Enskog-Wilke-Lee model.

The parameters ρmv and Vmv are obtained from the Redlich-Kwong equation-
of-state model.
You must supply parameters for these two models.
Subscript i denotes a diffusing component. j denotes a solvent.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
VC Vci — x 0.001 3.5 MOLE-VOLUME

References
R.C. Reid, J.M. Prausnitz, and T.K. Sherwood. The Properties of Gases and
Liquids, 3rd ed., (New York: McGraw-Hill, 1977), pp. 560-565.

Dawson-Khoury-Kobayashi (Mixture)
The diffusion coefficient of a gas into a gas mixture at high pressure is
calculated using an equation of Bird, Stewart, and Lightfoot by default (option
code 0):

244 3 Transport Property Models


If the first option code is set to 1, Blanc's law is used instead:

The binary diffusion coefficient Dijv at high pressures is calculated from the
Dawson-Khoury-Kobayashi model. (See Dawson-Khoury-Kobayashi (Binary).)
At low pressures (up to 1 atm) the binary diffusion coefficient is instead
calculated by the Chapman-Enskog-Wilke-Lee (Binary) model.
You must provide parameters for this model.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
DVBLNC — 1 — — — —

DVBLNC is set to 1 for a diffusing component and 0 for a nondiffusing


component.

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 597.

Nernst-Hartley
The effective diffusivity of an ion i in a liquid mixture with electrolytes can be
calculated using the Nernst-Hartley model:
(1)

Where:
F = 9.65x107C/kmole (Faraday's number)
xk = Mole fraction of any molecular species k
zi = Charge number of species i
The binary diffusion coefficient of the ion with respect to a molecular species
is set equal to the effective diffusivity of the ion in the liquid mixture:
(2)

The binary diffusion coefficient of an ion i with respect to an ion j is set to the
mean of the effective diffusivities of the two ions:

3 Transport Property Models 245


The diffusivity for molecular species is calculated by the Wilke-Chang
(Mixture) model.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
CHARGE z 0.0 — — —
IONMOB/1 l1 —† — — AREA, MOLES
IONMOB/2 l2 0.0 — — AREA, MOLES,
TEMPERATURE

†When IONMOB/1 is missing, the Nernst-Hartley model uses a nominal value


of 5.0 and issues a warning. This parameter should be specified for ions, and
not allowed to default to this value.

References
A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis
Horwood, Ltd, 1985).

Wilke-Chang (Binary)
The Wilke-Chang model calculates the liquid diffusion coefficient of
component i in a mixture at finite concentrations:

Dijl = Djil
The equation for the Wilke-Chang model at infinite dilution is:

Where i is the diffusing solute and j the solvent, and:

ϕj = Association factor of solvent. 2.26 for water, 1.90


for methanol, 1.50 for ethanol, 1.20 for propyl
alchohols and n-butanol, and 1.00 for all other
solvents.
Vbi = Liquid molar volume at Tb of solvent i

ηjl = Liquid viscosity of the solvent. This can be obtained


from the Andrade/DIPPR model. You must provide
parameters for one of these models.

ηl = Liquid viscosity of the complete mixture of n


components

246 3 Transport Property Models


x i, x j = Apparent binary mole fractions. If the actual mole

fractions are then

Parameter Symbol Default Lower Upper Units


Name/Element Limit Limit
MW Mj — 1.0 5000.0 —
VB Vbi*,l — 0.001 3.5 MOLE-VOLUME

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 598–600.

Wilke-Chang (Mixture)
The Wilke-Chang model calculates the liquid diffusion coefficient of
component i in a mixture.
The equation for the Wilke-Chang model is:

With:

Where:

ϕj = Association factor of solvent. 2.26 for water, 1.90 for


methanol, 1.50 for ethanol, 1.20 for propyl alchohols
and n-butanol, and 1.00 for all other solvents.
nl = Mixture liquid viscosity of all nondiffusing
components. This can be obtained from the
Andrade/DIPPR or another liquid mixture viscosity
model. You must provide parameters for one of
these models.
The parameter DLWC specifies which components diffuse. It is set to 1 for a
diffusing component and 0 for a non-diffusing component.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
MW Mj — 1.0 5000.0 —

3 Transport Property Models 247


Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
VB Vbi*,l — 0.001 3.5 MOLE-VOLUME
DLWC — 1 — — —

References
R.C. Reid, J.M. Praunsnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th ed., (New York: McGraw-Hill, 1987), p. 618.

Surface Tension Models


The Aspen Physical Property System has the following built-in surface tension
models.This section describes the surface tension models available.
Model Type
Liquid Mixture Surface Tension Liquid-vapor
API Liquid-vapor
IAPS Water-stream
Hakim-Steinberg-Stiel/DIPPR/IK-CAPE Liquid-vapor
Onsager-Samaras Electrolyte Correction Electrolyte liquid-vapor
Modified MacLeod-Sugden Liquid-vapor

Liquid Mixture Surface Tension


The liquid mixture surface tension is calculated using a general weighted
average expression (R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties
of Gases and Liquids, 4th. ed., New York: McGraw-Hill, 1987, p. 643):

Where:
x = Mole fraction
r = Exponent (specified by the option code)
Hadden (S. T. Hadden, Hydrocarbon Process Petrol Refiner, 45(10), 1966, p.
161) suggested that the exponent value r =1 should be used for most
hydrocarbon mixtures. However, Reid recommended the value of r in the
range of -1 to -3. The exponent value r can be specified using the model’s
Option Code (option code = 1, -1, -2, ..., -9 corresponding to the value of r).
The default value of r for this model is 1.

The pure component liquid surface tension σi*,l can be calculated by these
models:
• Hakim-Steinberg-Stiel
• DIPPR
• IK-CAPE

248 3 Transport Property Models


API Surface Tension
The liquid mixture surface tension for hydrocarbons is calculated using the
API model. This model is recommended for petroleum and petrochemical
applications. It is used in the CHAO-SEA, GRAYSON, LK-PLOCK, PENG-ROB,
and RK-SOAVE option sets. The general form of the model is:

Where:
fcn = A correlation based on API Procedure 10A32 (API Technical Data
Book, Petroleum Refining, 4th edition)

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
TB Tbi — — 4.0 2000.0 TEMPERATURE
SG SG — — 0.1 2.0 —
TC Tci — — 5.0 2000 TEMPERATURE

IAPS Surface Tension for Water


The IAPS surface tension model was developed by the International
Association for Properties of Steam. It calculates liquid surface tension for
water and steam. This model is used in option sets STEAMNBS and STEAM-
TA.
The general form of the equation for the IAPS surface tension model is:

σw=fcn(T, p)
Where:
fcn = Correlation developed by IAPS
The model is only applicable to water. No parameters are required.

Hakim-Steinberg-Stiel/DIPPR/PPDS/IK-
CAPE Liquid Surface Tension
The Aspen Physical Property System has several submodels for calculating
liquid surface tension. It uses parameter TRNSWT/5 to determine which
submodel is used. See Pure Component Temperature-Dependent Properties
for details.
If TRNSWT/5 is This equation is used And this parameter is
used
0 Hakim-Steinberg-Stiel —
106 DIPPR SIGDIP

3 Transport Property Models 249


If TRNSWT/5 is This equation is used And this parameter is
used
301 PPDS SIGPDS
401 IK-CAPE polynomial SIGPO
equation
505 NIST TDE Watson SIGTDEW
equation
511 NIST TDE expansion SIGISTE
512 NIST PPDS14 Equation SIGPDS14

Hakim-Steinberg-Stiel
The Hakim-Steinberg-Stiel equation is:

Where:
Qpi =

mi =

The parameter χi is the Stiel polar factor.


Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
TC Tci — 5.0 2000.0 TEMPERATURE
PC pci — PRESSURE

OMEGA ωi — -0.5 2.0 —

CHI χi 0 — — —

DIPPR Liquid Surface Tension


The DIPPR equation for liquid surface tension is:

Where:
Tri = T / Tci

Linear extrapolation of σi*,l versus T occurs outside of bounds.


(Other DIPPR equations may sometimes be used. See Pure Component
Temperature-Dependent Properties for details.)
The DIPPR model is used by PCES when estimating liquid surface tension.

Note: Reduced temperature Tr is always calculated using absolute


temperature units.

250 3 Transport Property Models


Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
SIGDIP/1 C1i — — — SURFACE-
TENSION
SIGDIP/2, ..., 5 C2i, ..., C5i 0 — — —
SIGDIP/6 C6i 0 — — TEMPERATURE
SIGDIP/7 C7i 1000 — — TEMPERATURE

PPDS
The equation is:

Linear extrapolation of σi*,l versus T occurs outside of bounds.


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
SIGPDS/1 C1i — — — — SURFACE-
TENSION
SIGPDS/2 C2i 0 — — — —
SIGPDS/3 C3i 0 — — — —
SIGPDS/4 C4i 0 — — — TEMPERATURE
SIGPDS/5 C5i 1000 — — — TEMPERATURE

NIST PPDS14 Equation


This equation is the same as the PPDS equation above, but it uses its own
parameter set which includes critical temperature.
Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
SIGPDS14/1 C1i — x — — N/m
SIGPDS14/2 C2i 0 x — — —
SIGPDS14/3 C3i 0 x — — —
SIGPDS14/4 Tci — x — — TEMPERATURE
SIGPDS14/5 C4i 0 x — — TEMPERATURE
SIGPDS14/6 C5i 1000 x — — TEMPERATURE

IK-CAPE Polynomial
The IK-CAPE equation is:

Linear extrapolation of σi*,l versus T occurs outside of bounds.

3 Transport Property Models 251


Parameter Symbol Default MDS Lower Upper Units
Name/Element Limit Limit
SIGPO/1 C1i — x — — SURFACE-
TENSION
SIGPO/2, ..., 10 C2i, ..., C10i 0 x — — SURFACE-
TENSION
TEMPERATURE
SIGPO/11 C11i 0 x — — TEMPERATURE
SIGPO/12 C12i 1000 x — — TEMPERATURE

NIST TDE Watson Equation


This equation can be used when parameter SIGTDEW is available.

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
SIGTDEW/1 C1i — x — — —
SIGTDEW/2, 3, 4 C2i, C3i, C4i 0 x — — —
SIGTDEW/5 Tc — x — — TEMPERATURE
SIGTDEW/6 nTerms 4 x — — —
SIGTDEW/7 Tlower 0 x — — TEMPERATURE
SIGTDEW/8 Tupper 1000 x — — TEMPERATURE

NIST TDE Expansion


This equation can be used when parameter SIGISTE is available.

Parameter Symbol Default MDS Lower Upper Units


Name/Element Limit Limit
SIGISTE/1 C1i — x — — N/m
SIGISTE/2, 3, 4 C2i, C3i, C4i 0 x — — N/m
SIGISTE/5 Tci — x — — TEMPERATURE
SIGISTE/6 nTerms 4 x — — —
SIGISTE/7 Tlower 0 x — — TEMPERATURE
SIGISTE/8 Tupper 1000 x — — TEMPERATURE

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 4th. ed., (New York: McGraw-Hill, 1987), p. 638.

252 3 Transport Property Models


Onsager-Samaras
The Onsager-Samaras model calculates the correction to the liquid mixture
surface tension of a solvent mixture, due to the presence of electrolytes:
for salt concentration < 0.03 (1)
M

Where:

σsolv = Surface tension of the solvent mixture calculated


by the Hakim-Steinberg-Stiel model
xcaa = Mole fraction of the apparent electrolyte ca

Δσca = Contribution to the surface tension correction due


to apparent electrolyte ca
For each apparent electrolyte ca, the contribution to the surface tension
correction is calculated as:
(2)

Where:

εsolv = Dielectric constant of the solvent mixture

ccaa =

Vml = Liquid molar volume calculated by the Clarke


model
Apparent electrolyte mole fractions are computed from the true ion mole-
fractions and ionic charge number. They are also computed if you use the
apparent component approach. See Apparent Component and True
Component Approaches in the Electrolyte Calculation chapter for a more
detailed discussion of this method.
Above salt concentration 0.03 M, the slope of surface tension vs. mole
fraction is taken to be constant at the value from 0.03 M.
You must provide parameters for the Hakim-Steinberg-Stiel model, used for
the calculation of the surface tension of the solvent mixture.
Parameter Symbol Default Lower Upper Units
Name/Element Limit Limit
CHARGE z 0.0 — — —

References
A. L. Horvath, Handbook of Aqueous Electrolyte Solutions, (Chichester: Ellis,
Ltd. 1985).

3 Transport Property Models 253


Modified MacLeod-Sugden
The modified MacLeod-Sugden equation for mixture liquid surface tension can
be derived from the standard MacLeod-Sugden equation by assuming that the
density of the vapor phase is zero. The modified MacLeod-Sugden equation is:

Where:

σi*,l = Surface tension for pure component i, calculated using


the Hakim-Steinberg-Stiel/DIPPR/IK-CAPE model.
Vi*,l = Liquid molar volume for pure component i, calculated
using the Rackett/DIPPR/IK-CAPE model.
l
V = Mixture liquid molar volume, calculated using the
Rackett model.

References
R.C. Reid, J.M. Prausnitz, and B.E. Poling, The Properties of Gases and
Liquids, 3rd. ed., (New York: McGraw-Hill, 1977).

254 3 Transport Property Models


4 Nonconventional Solid
Property Models

This section describes the nonconventional solid density and enthalpy models
available in the Aspen Physical Property System. The following table lists the
available models and their model names. Nonconventional components are
solid components that cannot be characterized by a molecular formula. These
components are treated as pure components, though they are complex
mixtures.

Nonconventional Solid Property Models


General Enthalpy and Model name Phase(s)
Density Models
General density polynomial DNSTYGEN S
General heat capacity ENTHGEN S
polynomial
Enthalpy and Density Model name Phase(s)
Models for Coal and Char
General coal enthalpy model HCOALGEN S
IGT coal density model DCOALIGT S
IGT char density model DCHARIGT S

General Enthalpy and Density


Models
The Aspen Physical Property System has two built-in general enthalpy and
density models. This section describes the general enthalpy and density
models available:

4 Nonconventional Solid Property Models 255


General Density Polynomial
DNSTYGEN is a general model that gives the density of any nonconventional
solid component. It uses a simple mass fraction weighted average for the
reciprocal temperature-dependent specific densities of its individual
constituents. There may be up to twenty constituents with mass percentages.
You must define these constituents, using the general component attribute
GENANAL. The equations are:

Where:
wij = Mass fraction of the jth constituent in component i

ρijs = Density of the jth consituent in component i

Parameter Symbol MDS Default Lower Upper Units


Name/Element Limit Limit
DENGEN/1, 5, 9, …, 77 ai,j1 x — — — MASS-ENTHALPY
and TEMPERATURE
DENGEN/2, 6, 10, …, ai,j2 x 0 — — MASS-ENTHALPY
78 and TEMPERATURE
DENGEN/3, 7, 11, …, ai,j3 x 0 — — MASS-ENTHALPY
79 and TEMPERATURE
DENGEN/4, 8, 12, …, ai,j4 x 0 — — MASS-ENTHALPY
80 and TEMPERATURE

Use the elements of GENANAL to input the mass percentages of the


constituents. The structure of DENGEN is: Elements 1 to 4 are the four
coefficients for the first constituent, elements 5 to 8 are the coefficients for
the second constitutent, and so on, for up to 20 constituents.

General Heat Capacity Polynomial


ENTHGEN is a general model that gives the specific enthalpy of any
nonconventional component as a simple mass-fraction-weighted-average for
the enthalpies of its individual constituents. You may define up to twenty
constituents with mass percentages, using the general component attribute
GENANAL. The specific enthalpy of each constituent at any temperature is
calculated by combining specific enthalpy of formation of the solid with a
sensible heat change. (See Nonconventional Component Enthalpy Calculation
in Physical Property Methods.)
The equations are:

256 4 Nonconventional Solid Property Models


Where:
wij = Mass fraction of the jth constituent in
component i
hi s = Specific enthalpy of solid component i

Δfhjs = Specific enthalpy of formation of constituent j

Cps = Heat capacity of the jth constituent in


component i

Parameter Symbol MDS Default Lower Upper Units


Name/Element Limit Limit
DHFGEN/J Δfhjs x 0 — — MASS-ENTHALPY

HCGEN/1, 5, 9, …, 77 ai,j1 x — — — MASS-ENTHALPY


and
TEMPERATURE
HCGEN/2, 6, 10, …, 78 ai,j2 x 0 — — MASS-ENTHALPY
and
TEMPERATURE
HCGEN/3, 7, 11, …, 79 ai,j3 x 0 — — MASS-ENTHALPY
and
TEMPERATURE
HCGEN/4, 8, 12, …, 80 ai,j4 x 0 — — MASS-ENTHALPY
and
TEMPERATURE

The elements of GENANAL are used to input the mass percentages of the
constituents. The structure for HCGEN is: Elements 1 to 4 are the four
coefficients for the first constituent, elements 5 to 8 are the coefficients for
the second constitutent, and so on, for up to 20 constituents.

Enthalpy and Density Models


for Coal and Char
Coal is modeled in the Aspen Physical Property System as a nonconventional
solid. Coal models are empirical correlations, which require solid material
characterization information. Component attributes are derived from
constituent analyses. Definitions of coal component attributes are given in the
Aspen Plus User Guide, Chapter 6.
Enthalpy and density are the only properties calculated for nonconventional
solids. This section describes the special models available in the Aspen
Physical Property System for the enthalpy and density of coal and char. The

4 Nonconventional Solid Property Models 257


component attributes required by each model are included. The coal models
are:
• General coal enthalpy
• IGT Coal Density
• IGT Char Density
• User models for density and enthalpy. See User Models for
Nonconventional Properties in Chapter 6 of Aspen Plus User Models, for
details on writing the subroutines for these user models.

Notation
Most correlations for the calculation of coal properties require proximate,
ultimate, and other analyses. These are converted to a dry, mineral-matter-
free basis. Only the organic portion of the coal is considered.
Moisture corrections are made for all analyses except hydrogen, according to
the formula:

Where:
w = The value determined for weight fraction
d
w = The value on a dry basis
= The moisture weight fraction

For hydrogen, the formula includes a correction for free-moisture hydrogen:

The mineral matter content is calculated using the modified Parr formula:

The ash term corrects for water lost by decomposition of clays in the ash
determination. The average water constitution of clays is assumed to be 11.2
percent. The sulfur term allows for loss in weight of pyritic sulfur when pyrite
is burned to ferric oxide. The original Parr formula assumed that all sulfur is
pyritic sulfur. This formula included sulfatic and organic sulfur in the mineral-
matter calculation. When information regarding the forms of sulfur is
available, use the modified Parr formula to give a better approximation of the
percent of inorganic material present. Because chlorine is usually small for
United States coals, you can omit chlorine from the calculation.
Correct analyses from a dry basis to a dry, mineral-matter-free basis, using
the formula:

Where:

258 4 Nonconventional Solid Property Models


Δwd = Correction factor for other losses, such as the loss
of carbon in carbonates and the loss of hydrogen
present in the water constitution of clays

The oxygen and organic sulfur contents are usually calculated by difference
as:

Where:
Cp = Heat capacity / (J/kgK)
cp = Heat capacity / (cal/gC)
h = Specific enthalpy

Δch = Specific heat of combustion

Δfh = Specific heat of formation

Ro = Mean-maximum relectance in oil


T = Temperature/K
t = Temperature/C
w = Weight fraction

ρ = Specific density

Subscripts:
A = Ash
C = Carbon
Cl = Chlorine
FC = Fixed carbon
H = Hydrogen
H2O = Moisture
MM = Mineral matter
N = Nitrogen
O = Oxygen
So = Organic sulfur
Sp = Pyritic sulfur
St = Total sulfur

4 Nonconventional Solid Property Models 259


S = Other sulfur
VM = Volatile matter
Superscripts:
d = Dry basis
m = Mineral-matter-free basis

General Coal Enthalpy Model


The general coal model for computing enthalpy in the Aspen Physical Property
System is HCOALGEN. This model includes a number of different correlations
for the following:
• Heat of combustion
• Heat of formation
• Heat capacity
You can select one of these correlations using an option code in the Properties
Advanced NC-Props form. (See the Aspen Plus User Guide, Chapter 6). Use
option codes to specify a calculation method for properties. Each element in
the option code vector is used in the calculation of a different property.
The table labeled HCOALGEN Option Codes (below) lists model option codes
for HCOALGEN. The table is followed by a detailed description of the
calculations used for each correlation.
The correlations are described in the following section. The component
attributes are defined in Aspen Plus User Guide, Chapter 6.

Heat of Combustion Correlations


The heat of combustion of coal in the HCOALGEN model is a gross calorific
value. It is expressed in Btu/lb of coal on a dry mineral-matter-free basis.
ASTM Standard D-2015 defines standard conditions for measuring gross
calorific value. Initial oxygen pressure is 20 to 40 atmospheres. Products are
in the form of ash; liquid water; and gaseous CO2, SO2, and NO2.
You can calculate net calorific value from gross calorific value by making a
deduction for the latent heat of vaporization of water.
Heat of combustion values are converted back to a dry, mineral-matter-
containing basis with a correction for the heat of combustion of pyrite. The
formula is:

The heat of combustion correlations were evaluated by the Institute of Gas


Technology (IGT). They used data for 121 samples of coal from the Penn
State Data Base (IGT, 1976) and 457 samples from a USGS report (Swanson,
et al., 1976). These samples included a wide range of United States coal
fields. The constant terms in the HCOALGEN correlations are bias corrections
obtained from the IGT study.

260 4 Nonconventional Solid Property Models


Boie Correlation:

Parameter Name/Element Symbol Default


BOIEC/1 a1i 151.2
BOIEC/2 a2i 499.77
BOIEC/3 a3i 45.0
BOIEC/4 a4i -47.7
BOIEC/5 a5i 27.0
BOIEC/6 a6i -189.0

Dulong Correlation:

Parameter Name/Element Symbol Default


DLNGC/1 a1i 145.44
DLNGC/2 a2i 620.28
DLNGC/3 a3i 40.5
DLNGC/4 a4i -77.54
DLNGC/5 a5i -16.0

Grummel and Davis Correlation:

Parameter Name/Element Symbol Default


GMLDC/1 a1i 0.3333
GMLDC/2 a2i 654.3
GMLDC/3 a3i 0.125
GMLDC/4 a4i 0.125
GMLDC/5 a5i 424.62
GMLDC/6 a6i -2.0

Mott and Spooner Correlation:

Parameter Name/Element Symbol Default


MTSPC/1 a1i 144.54
MTSPC/2 a2i 610.2
MTSPC/3 a3i 40.3
MTSPC/4 a4i 62.45
MTSPC/5 a5i 30.96
MTSPC/6 a6i 65.88

4 Nonconventional Solid Property Models 261


Parameter Name/Element Symbol Default
MTSPC/7 a7i -47.0

IGT Correlation:

Parameter Name/Element Symbol Default


CIGTC/1 a1i 178.11
CIGTC/2 a2i 620.31
CIGTC/3 a3i 80.93
CIGTC/4 a4i 44.95
CIGTC/5 a5i -5153.0

User Input Value of Heat Combustion


Parameter Name/Element Symbol Default
HCOMB Δchid 0

Standard Heat of Formation Correlations


There are two standard heat of formation correlations for the HCOALGEN
model:
• Heat of combustion-based
• Direct
Heat of Combustion-Based Correlation This is based on the assumption that
combustion results in complete oxidation of all elements except sulfatic sulfur
and ash, which are considered inert. The numerical coefficients are
combinations of stoichiometric coefficients and heat of formation for CO2,
H2O, HCl, and NO2 at 298.15K:

Direct Correlation Normally small, relative to its heat of combustion. An error


of 1% in the heat of a combustion-based correlation produces about a 50%
error when it is used to calculate the heat of formation. For this reason, the
following direct correlation was developed, using data from the Penn State
Data Base. It has a standard deviation of 112.5 Btu/lb, which is close to the
limit, due to measurement in the heat of combustion:

Where:

262 4 Nonconventional Solid Property Models


Parameter Name/Element Symbol Default
HFC/1 a1i 1810.123
HFC/2 a2i -502.222
HFC/3 a3i 329.1087
HFC/4 a4i 121.766
HFC/5 a5i -542.393
HFC/6 a6i 1601.573
HFC/7 a7i 424.25
HFC/8 a8i -525.199
HFC/9 a9i -11.4805
HFC/10 a10i 31.585
HFC/11 a11i 13.5256
HFC/12 a12i 11.5
HFC/13 a13i -685.846
HFC/14 a14i -22.494
HFC/15 a15i -64836.19

Heat Capacity Kirov Correlations


The Kirov correlation (1965) considered coal to be a mixture of moisture, ash,
fixed carbon, and primary and secondary volatile matter. Secondary volatile
matter is any volatile matter up to 10% on a dry, ash-free basis; the
remaining volatile matter is primary. The correlation developed by Kirov
treats the heat capacity as a weighted sum of the heat capacities of the
constituents:

Where:
i = Component index
j = Constituent index j = 1, 2 , ... , ncn
Where the values of j represent:
1 Moisture
2 Fixed carbon
3 Primary volatile matter
4 Secondary volatile matter
5 Ash
wj = Mass fraction of jth constituent on dry basis
This correlation calculates heat capacity in cal/gram-C using temperature in
C. The parameters must be specified in appropriate units for this conversion.

4 Nonconventional Solid Property Models 263


Parameter Name/Element Symbol Default
CP1C/1 ai,11 1.0
CP1C/2 ai,12 0
CP1C/3 ai,13 0
CP1C/4 ai,14 0
CP1C/5 ai,21 0.165
CP1C/6 ai,22

CP1C/7 ai,23

CP1C/8 ai,24 0
CP1C/9 ai,31 0.395
CP1C/10 ai,32
CP1C/11 ai,33 0
CP1C/12 ai,34 0
CP1C/13 ai,41 0.71
CP1C/14 ai,42

CP1C/15 ai,43 0
CP1C/16 ai,44 0
CP1C/17 ai,51 0.18
CP1C/18 ai,52

CP1C/19 ai,53 0
CP1C/20 ai,54 0

Cubic Temperature Equation


The cubic temperature equation is:

Parameter Name/Element Symbol Default


CP2C/1 a1i 0.438
CP2C/2 a2i

CP2C/3 a3i
CP2C/4 a4i

The default values of the parameters were developed by Gomez, Gayle, and
Taylor (1965). They used selected data from three lignites and a
subbituminous B coal, over a temperature range from 32.7 to 176.8°C.

HCOALGEN Option Codes


Option Code Option Code Calculation Parameter Component
Number Value† Method Names Attributes
1 Heat of Combustion
1 Boie correlation BOIEC ULTANAL
SULFANAL
PROXANAL

264 4 Nonconventional Solid Property Models


Option Code Option Code Calculation Parameter Component
Number Value† Method Names Attributes
1 Heat of Combustion
2 Dulong DLNGC ULTANAL
correlation SULFANAL
PROXANAL
3 Grummel and GMLDC ULTANAL
Davis correlation SULFANAL
PROXANAL
4 Mott and Spooner MTSPC ULTANAL
correlation SULFANAL
PROXANAL
5 IGT correlation CIGTC ULTANAL
PROXANAL
6 User input value HCOMB ULTANAL
PROXANAL
2 Standard Heat of Formation
1 Heat-of- — ULTANAL
combustion- SULFANAL
based correlation
2 Direct correlation HFC ULTANAL
SULFANAL
PROXANAL
3 Heat Capacity
1 Kirov correlation CP1C PROXANAL
2 Cubic CP2C —
temperature
equation
4 Enthalpy Basis
1 Elements in their — —
standard states — —
at 298.15K and 1
atm
2 Component at — —
298.15 K

Default = 1 for each option code

References
Gomez, M., J.B. Gayle, and A.R. Taylor, Jr., Heat Content and Specific Heat of
Coals and Related Products, U.S. Bureau of Mines, R.I. 6607, 1965.
IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data
Book, Section PMa. 44.1, 1976.
Kirov, N.Y., "Specific Heats and Total Heat Contents of Coals and Related
Materials are Elevated Temperatures," BCURA Monthly Bulletin, (1965),
pp. 29, 33.
Swanson, V.E. et al., Collection, Chemical Analysis and Evaluation of Coal
Samples in 1975, U.S. Geological Survey, Open-File Report (1976), pp. 76–
468.

4 Nonconventional Solid Property Models 265


IGT Coal Density Model
The DCOALIGT model gives the true (skeletal or solid-phase) density of coal
on a dry basis. It uses ultimate and sulfur analyses. The model is based on
equations from IGT (1976):

The equation for ρidm is good for a wide range of hydrogen contents, including
anthracities and high temperature cokes. The standard deviation of this
correlation for a set of 190 points collected by IGT from the literature was
12x10-6 m3/kg. The points are essentially uniform over the whole range. This
is equivalent to a standard deviation of about 1.6% for a coal having a
hydrogen content of 5%. It increases to about 2.2% for a coke or anthracite
having a hydrogen content of 1%.
Parameter Name/Element Symbol Default
DENIGT/1 a1i 0.4397
DENIGT/2 a2i 0.1223
DENIGT/3 a3i -0.01715
DENIGT/4 a4i 0.001077

Reference
IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data
Book, Section PMa. 44.1, 1976.

IGT Char Density Model


The DGHARIGT model gives the true (skeletal or solid-phase) density of char
or coke on a dry basis. It uses ultimate and sulfur analyses. This model is
based on equations from IGT (1976):

266 4 Nonconventional Solid Property Models


Parameter Name/Element Symbol Default
DENIGT/1 a1i 0.4397
DENIGT/2 a2i 0.1223
DENIGT/3 a3i -0.01715
DENIGT/4 a4i 0.001077

The densities of graphitic high-temperature carbons (including cokes) range


from 2.2x103 to 2.26x103 kg/m3. Densities of nongraphitic high-temperature
carbons (derived from chars) range from 2.0x103 to 2.2x103 kg/m3. Most of
the data used in developing this correlation were for carbonized coking coals.
Although data on a few chars (carbonized non-coking coals) were included,
none has a hydrogen content less than 2%. The correlation is probably not
accurate for high temperature chars.

References
I.M. Chang, B.S. Thesis, Massachusetts Institute of Technology, 1979.
M. Gomez, J.B. Gayle, and A.R. Taylor, Jr., Heat Content and Specific Heat of
Coals and Related Products, U.S. Bureau of Mines, R.I. 6607, 1965.
IGT (Institute of Gas Technology), Coal Conversion Systems Technical Data
Book, Section PMa. 44.1, 1976.
N.Y. Kirov, "Specific Heats and Total Heat Contents of Coals and Related
Materials are Elevated Temperatures," BCURA Monthly Bulletin, (1965),
pp. 29, 33.
V.E. Swanson et al., Collection, Chemical Analysis and Evaluation of Coal
Samples in 1975, U.S. Geological Survey, Open-File Report (1976), pp. 76–
468.

4 Nonconventional Solid Property Models 267


5 Property Model Option
Codes

The following tables list the model option codes available:


• Option Codes for Transport Property Models
• Option Codes for Activity Coefficient Models
• Option Codes for Equation of State Models
• Option Codes for K-value Models
• Option Codes for Enthalpy Models
• Option Codes for Gibbs Energy Models
• Option Codes for Molar Volume Models

Option Codes for Transport


Property Models
Model Name Option Value Descriptions
Code
SIG2HSS 1 1 Exponent in mixing rule (default)
-1,-2, Exponent in mixing rule
..., -9
SIG2ONSG 1 1 Exponent in mixing rule (default)
-1,-2, Exponent in mixing rule
..., -9
MUL2API, 1 0 Release 9 method. First, the API, SG of the
MULAPI92 mixture is calculated, then the API correlation is
used (default)
1 Pre-release 9 method. Liquid viscosity is
calculated for each pseudocomponent using the
API method. Then mixture viscosity is
calculated by mixing rules.
MUL2ANDR, 1 0 Mixture viscosity weighted by mole fraction
DL0WCA, DL1WCA, (default)
DL0NST, DL1NST

268 5 Property Model Option Codes


Model Name Option Value Descriptions
Code
1 Mixture viscosity weighted by mass fraction

MUL2JONS 1 0 Mixture viscosity weighted by mole fraction


(default)
1 Mixture viscosity weighted by mass fraction
2 0 Use Breslau and Miller equation instead of Jones
and Dole equation when electrolyte
concentration exceeds 0.1 M.
1 Always use Jones and Dole equation when the
parameters are available.
3 0 Solvent liquid mixture viscosity from Andrade
liquid mixture viscosity model (default)
1 Solvent liquid mixture viscosity from quadratic
mixing rule
2 Solvent liquid mixture viscosity from Aspen
liquid mixture viscosity model
MUL2CLS, 1 0 Original correlation
MUL2CLS2
1 Modified UOP correlation
MUL2QUAD 1 0 Use mole basis composition (default)
1 Use mass basis composition
KL2VR, KL2RDL 1 0 Do not check ratio of KL max / KL min

1 Check ratio. If KL max / KL min > 2, set


exponent to 1, overriding option code 2.
2 0 Exponent is -2
1 Exponent is 0.4
2 Exponent is 1. This uses a weighted average of
liquid thermal conductivities.

Option Codes for Activity


Coefficient Models
Model Name Option Value Descriptions
Code
GMXSH 1 0 No volume term (default)
1 Includes volume term
WHENRY 1 1 Equal weighting
2 Size - VC1/3
3 Area - VC2/3 (default)
4 Volume - VC
Electrolyte NRTL Activity Coefficient Model (GMENRTL, GMELC, GMENRHG)
1 Defaults for pair parameters

5 Property Model Option Codes 269


Model Name Option Value Descriptions
Code
1 Pair parameters default to zero
2 Solvent/solute pair parameters default to water
parameters. Water/solute pair parameters
default to zero (default for GMELC)
3 Default water parameters to 8, -4. Default
solvent/solute parameters to 10, -2 (default for
GMENRTL and GMENRHG)
2 Vapor phase equation-of-state for liquid enthalpy
and Gibbs energy of HF
0 Ideal gas EOS (default)
1 HF EOS for hydrogen fluoride
3 Solvent/solvent binary parameter values
obtained from
0 Scalar GMELCA, GMELCB and GMELCM (default
for GMELC)
1 Vector NRTL(8) (default for GMENRTL and
GMENRHG)
4 Enthalpy calculation method
0 Electrolyte NRTL Enthalpy (default for GMELC)
1 Helgeson method (default for GMENRTL and
GMENRHG)
5 Vapor phase enthalpy departure contribution to
liquid enthalpy. Hliq = Hig + DHV - ΔHvap; this
option indicates how DHV is calculated.
0 Do not calculate (DHV=0) (default)
1 Calculate using Redlich-Kwong equation of state
2 Calculate using Hayden-O'Connell equation of
state
6 Method for calculating corresponding states (for
handling solvents that exist in both subcritical
and supercritical conditions)
0 Original method (default)
1 Corresponding state method. Calculates a
pseudo-critical temperature of the solvents and
uses it together with the actual critical
temperatures of the pure solvents to adjust the
liquid enthalpy departure. This results in a
smoother transition of the liquid enthalpy
contribution when the component transforms
from subcritical to supercritical.
GMPT1 1 Defaults for pair mixing rule
-1 No unsymmetric mixing
0 Unsymmetric mixing polynomial (default)
1 Unsymmetric mixing integral
GAQPT3, GMPT3, 1 Defaults for pair mixing rule
HAQPT3 -1 No unsymmetric mixing
0 Unsymmetric mixing polynomial (default)

270 5 Property Model Option Codes


Model Name Option Value Descriptions
Code
1 Unsymmetric mixing integral
2 Standard enthalpy calculation
0 Standard electrolytes method (Pre-release 10)
1 Helgeson method (Default)
3 Estimation of K-stoic temperature dependency
0 Use value at 298.15 K
1 Helgeson Method (default)
1 Reference temperature usage
COSMOSAC
1 Model choice
1 COSMO-SAC model by Lin and Sandler (2002)
(Default)
2 COSMO-RS model by Klamt and Eckert (2000)
3 Lin and Sandler model with modified exchange
energy (Lin et al., 2002)
HS0POL1, GS0POL1, SS0POL1 (Solid pure component polynomials)
1 0 Use standard reference temperature (default)
1 Use liquid reference temperature
Hansen
1 0 Hansen volume input by user (default)
1 Hansen volume calculated by Aspen Plus
NRTL-SAC (patent pending), ENRTL-SAC (patent pending)
1 0 Flory-Huggins term included (default)
1 Flory-Huggins term removed
PHILELC
1 Steam table for liquid enthalpy of water
0 Use steam table for liquid enthalpy of water
(default)
1 Use specified EOS model
2 Vapor phase equation-of-state for liquid enthalpy
of HF
0 Use specified EOS model (default)
1 HF EOS for hydrogen fluoride

Option Codes for Equation of


State Models
Model Name Option Value Descriptions
Code
ESBWRS, ESBWRS0 1 0 Do not use steam tables
1 Calculate properties (H, S, G, V) of water from
steam table (default; see Note)

5 Property Model Option Codes 271


Model Name Option Value Descriptions
Code
2 0 Original RT-Opt root search method (default)
1 VPROOT/LQROOT Aspen Plus root search
method. Use this if the equation-oriented Aspen
Plus solution fails to converge and some
streams with missing phases show the same
properties for the missing phase as for another
phase.
ESHOC, ESHOC0, 1 0 Hayden-O'Connell model. Use chemical theory
PHV0HOC only if one component has HOCETA=4.5
(default)
1 Always use the chemical theory regardless of
HOCETA values
2 Never use the chemical theory regardless of
HOCETA values
2 0 Check high-pressure limit. If exceeded,
calculate volume at cut-off pressure.
1 Ignore high-pressure limit. Calculate volume
model T and P.
ESPR, ESPR0, 1 0 ASPEN Boston/Mathias alpha function when Tr
ESPRSTD, >1, original literature alpha function otherwise.
ESPRSTD0 (default for ESPR)
1 Original literature alpha function (default for
ESPRSTD)
2 Extended Gibbons-Laughton alpha function
3 Twu Generalized alpha function
4 Twu alpha function
2 0 Standard Peng-Robinson mixing rules (default)
1 Asymmetric Kij mixing rule from Dow

3 0 Do not use steam tables (default)


1 Calculate water properties (H, S, G, V) from
steam table (see Note)
4 0 Do not use Peneloux liquid volume correction
(default)
1 Apply Peneloux liquid volume correction (See
SRK)
5 0 Use analytical method for root finding (default)
1 Use RTO numerical method for root finding

2 Use VPROOT/LQROOT numerical method for


root finding
ESPRWS, 1 0 ASPEN Boston/Mathias alpha function
ESPRWS0, ESPRV1,
ESPRV10, ESPRV2,
ESPRV20,
ESPSAFT, 1 0 Random copolymer (default)
ESPSAFT0

272 5 Property Model Option Codes


Model Name Option Value Descriptions
Code
1 Alternative copolymer
2 Block copolymer
2 0 Do not use Sadowski's copolymer model
1 Use Sadowski's copolymer model in which a
copolymer must be built only by two different
types of segments
3 0 Use association term (default)
1 Do not use association term
ESRKS, ESRKS0, See Soave-Redlich-Kwong Option Codes
ESRKSTD,
ESRKSTD0, ESSRK,
ESSRK0, ESRKSML,
ESRKSML0
ESRKSW, ESRKSW0 1 0 ASPEN Boston/Mathias alpha function (default)
1 Original literature alpha function
2 Grabowski and Daubert alpha function for H2
above TC (α = 1.202 exp(-0.30228xTri))
ESRKU, ESRKU0 1 Initial temperature for binary parameter
estimation
0 At TREF=25 C (default)
1 The lower of TB(i) or TB(j)
2 (TB(i) + TB(j))/2
>2 Value entered used as temperature
2 VLE or LLE UNIFAC
0 VLE (default)
1 LLE
3 Property diagnostic level flag (-1 to 8)
4 Vapor phase EOS used in generation of TPxy
data with UNIFAC
0 Hayden-O'Connell (default)
1 Redlich-Kwong
5 Do/do not estimate binary parameters
0 Estimate (default)
1 Set to zero
ESHF, ESHF0 1 0 Equation form for Log(k) expression:
log(K) = A + B/T + C ln(T) + DT (default)
1 log(K) = A + B/T + CT + DT2 + E log(P)
1 Original literature alpha function
2 Mathias-Copeman alpha function
3 Schwartzentruber-Renon alpha function
(default)

5 Property Model Option Codes 273


Model Name Option Value Descriptions
Code
ESRKSWS, 1 Equation form for alpha function
ESRKSWS0,
ESRKSV1,
ESRKSV10,
ESRKSV2,
ESRKSV20,
1 Original literature alpha function
2 Mathias-Copeman alpha function
3 Schwartzentruber-Renon alpha function
(default)
ESSTEAM, 1 0 ASME 1967 correlations
ESSTEAM0
1 NBS 1984 equation of state (default)
2 NBS 1984 equation of state with alternate root
search method (STMNBS2)
2 0 Original fugacity and enthalpy calculations
when used with STMNBS2
1 Rigorous fugacity calculation from Gibbs energy
and corrected enthalpy departure (default)
ESH2O, ESH2O0 1 0 ASME 1967 correlations (default)
1 NBS 1984 equation of state
2 NBS 1984 equation of state with alternate root
search method (STMNBS2)

Note: The enthalpy, entropy, Gibbs energy, and molar volume of water are
calculated from the steam tables when the relevant option is enabled. The
total properties are mole-fraction averages of these values with the properties
calculated by the equation of state for other components. Fugacity coefficient
is not affected.

Soave-Redlich-Kwong Option
Codes
There are five related models all based on the Soave-Redlich-Kwong equation
of state which are very flexible and have many options. These models are:
• Standard Redlich-Kwong-Soave (ESRKSTD0, ESRKSTD)
• Redlich-Kwong-Soave-Boston-Mathias (ESRKS0, ESRKS)
• Soave-Redlich-Kwong (ESSRK, ESSRK0)
• SRK-Kabadi-Danner (ESSRK, ESSRK0)
• SRK-ML (ESRKSML, ESRKSML0)
The options for these models can be selected using the option codes
described in the following table:

274 5 Property Model Option Codes


Option Value Description
Code
1 0 Standard SRK alpha function for Tr < 1, Boston-Mathias alpha
function for Tr > 1
1 Standard SRK alpha function for all
2 Grabovsky – Daubert alpha function for H2 and standard SRK
alpha function for others (default)
3 Extended Gibbons-Laughton alpha function for all components
(see notes 1, 2, 3)
4 Mathias alpha function
5 Twu generalized alpha function
2 0 Standard SRK mixing rules (default except for SRK-Kabadi-
Danner)
1 Kabadi – Danner mixing rules (default for SRK-Kabadi-Danner)
(see notes 3, 4, 5)
3 0 Do not calculate water properties from steam table (default for
Redlich-Kwong-Soave models)
1 Calculate properties (H, S, G, V) of water from steam table
(default for SRK models; see note 6)
4 0 Do not apply the Peneloux liquid volume correction
1 Apply the liquid volume correction (default)
5 0 Use analytical method for root finding (default)
1 Use RTO numerical method for root finding
2 Use VPROOT/LQROOT numerical method for root finding
6 0 Use true logarithm in calculating properties (default for
Redlich-Kwong-Soave models)
1 Use smoothed logarithm in calculating properties (default for
SRK models)

Notes
1. The standard alpha function is always used for Helium.
2. If extended Gibbons-Laughton alpha function parameters are missing, the
Boston-Mathias extrapolation will be used if T > Tc, and the standard
alpha function will be used if T < Tc.
3. The extended Gibbons-Laughton alpha function should not be used with
the Kabadi-Danner mixing rules.
4. The Kabadi-Danner mixing rules should not be used if Lij parameters are
provided for water with any other components.
5. It is recommended that you use the SRK-KD property method rather than
change this option code.
6. The enthalpy, entropy, Gibbs energy, and molar volume of water are
calculated from the steam tables when this option is enabled. The total
properties are mole-fraction averages of these values with the properties
calculated by the equation of state for other components. Fugacity
coefficient is not affected.

5 Property Model Option Codes 275


Option Codes for K-Value
Models
Model Option Value Descriptions
Name Code
BK10 1 0 Treat pseudocomponents as paraffins (default)
1 Treat pseudocomponents as aromatics

Option Codes for Enthalpy


Models
Model Name Option Value Descriptions
Code
DHL0HREF 1 1 Use Liquid reference state for all components (Default)
2 Use liquid and gaseous reference states based on the
state of each component
Electrolyte NRTL Enthalpy (HMXENRTL, HAQELC, HMXELC, HMXENRHG)
1 Defaults for pair parameters
1 Pair parameters default to zero
2 Solvent/solute pair parameters default to water
parameters. Water/solute pair parameters default to
zero (default for ELC models)
3 Default water parameters to 8, -4. Default
solvent/solute parameters to 10, -2 (default for
HMXENRTL and HMXENRHG)
2 Vapor phase equation-of-state for liquid enthalpy and
Gibbs energy of HF
0 Ideal gas EOS (default)
1 HF EOS for hydrogen fluoride
3 Solvent/solvent binary parameter values obtained
from:
0 Scalar GMELCA, GMELCB and GMELCM (default for ELC
models)
1 Vector NRTL(8) (default for HMXENRTL and
HMXENRHG)
4 Enthalpy calculation method
0 Electrolyte NRTL Enthalpy (default for ELC models,
HMXENRTL, and ELECNRTL property method)
1 Helgeson method (default for HMXENRHG)
5 Vapor phase enthalpy departure contribution to liquid
enthalpy. Hliq = Hig + DHV - ΔHvap; this option indicates
how DHV is calculated.
0 Do not calculate (DHV=0) (default)
1 Calculate using Redlich-Kwong equation of state
2 Calculate using Hayden-O'Connell equation of state

276 5 Property Model Option Codes


Model Name Option Value Descriptions
Code
6 Method for calculating corresponding states (for
handling solvents that exist in both subcritical and
supercritical conditions)
0 Original method (default)
1 Corresponding state method. Calculates a pseudo-
critical temperature of the solvents and uses it
together with the actual critical temperatures of the
pure solvents to adjust the liquid enthalpy departure.
This results in a smoother transition of the liquid
enthalpy contribution when the component transforms
from subcritical to supercritical.
7 Method for handling Henry components and multiple
solvents
0 Pure liquid enthalpy calculated by aqueous infinite
dilution heat capacity; only water as solvent
1 Pure liquid enthalpy for Henry components calculated
using Henry's law; use this option when there are
multiple solvents.
HLRELNRT, HLRELELC
1 Defaults for pair parameters
1 Pair parameters default to zero
2 Solvent/solute pair parameters default to water
parameters. Water/solute pair parameters default to
zero (default for HLRELELC)
3 Default water parameters to 8, -4. Default
solvent/solute parameters to 10, -2 (default for
HLRENRTL)
2 Solvent/solvent binary parameter values obtained
from:
0 Scalar GMELCA, GMELCB and GMELCM (default)
1 Vector NRTL(8)
3 Mixture density model
0 Rackett equation with Campbell-Thodos modification
1 Quadratic mixing rule for molecular components (mole
basis)
HIG2ELC, HIG2HG
1 Enthalpy calculation method
0 Electrolyte NRTL Enthalpy (default for HIG2ELC)
1 Helgeson method (default for HIG2HG)
DHLELC
1 Steam table for liquid enthalpy of water
0 Use steam table for liquid enthalpy of water (default)
1 Use specified EOS model
2 Vapor phase equation-of-state for liquid enthalpy of HF
0 Use specified EOS model (default)
1 HF EOS for hydrogen fluoride

5 Property Model Option Codes 277


Option Codes for Gibbs Energy
Models
Model Name Option Value Descriptions
Code
Electrolyte NRTL Gibbs Energy (GMXENRTL, GAQELC, GMXELC, GMXENRHG)
1 Defaults for pair parameters
1 Pair parameters default to zero
2 Solvent/solute pair parameters default to water
parameters. Water/solute pair parameters
default to zero (default for ELC models)
3 Default water parameters to 8, -4. Default
solvent/solute parameters to 10, -2 (default for
GMXENRTL and GMXENRHG)
2 Vapor phase equation-of-state for liquid enthalpy
and Gibbs energy of HF
0 Ideal gas EOS (default)
1 HF EOS for hydrogen fluoride
3 Solvent/solvent binary parameter values
obtained from
0 Scalar GMELCA, GMELCB and GMELCM (default
for ELC models)
1 Vector NRTL(8) (default for GMXENRTL and
GMXENRHG)
4 Enthalpy calculation method
0 Electrolyte NRTL Enthalpy (default for ELC
models)
1 Helgeson method (default for GMXENRTL and
GMXENRHG)
5 Vapor phase enthalpy departure contribution to
liquid enthalpy. Hliq = Hig + DHV - ΔHvap; this
option indicates how DHV is calculated.
0 Do not calculate (DHV=0) (default)
1 Calculate using Redlich-Kwong equation of state
2 Calculate using Hayden-O'Connell equation of
state
6 Method for handling Henry components and
multiple solvents
0 Pure liquid enthalpy calculated by aqueous
infinite dilution heat capacity; only water as
solvent
1 Pure liquid enthalpy for Henry components
calculated using Henry's law; use this option
when there are multiple solvents.
GLRELNRT, GLRELELC
1 Defaults for pair parameters
1 Pair parameters default to zero

278 5 Property Model Option Codes


Model Name Option Value Descriptions
Code
2 Solvent/solute pair parameters default to water
parameters. Water/solute pair parameters
default to zero (default for GLRELELC)
3 Default water parameters to 8, -4. Default
solvent/solute parameters to 10, -2 (default for
GLRENRTL)
2 Solvent/solvent binary parameter values
obtained from:
0 Scalar GMELCA, GMELCB and GMELCM (default)
1 Vector NRTL(8)
3 Mixture density model
0 Rackett equation with Campbell-Thodos
modification
1 Quadratic mixing rule for molecular components
(mole basis)
GIG2ELC, GIG2HG
1 Enthalpy calculation method
0 Electrolyte NRTL Enthalpy (default for GIG2ELC)
1 Helgeson method (default for GIG2HG)

Option Codes for Liquid Volume


Models
Model Option Value Descriptions
Name Code
VL2QUAD 1 0 Use normal pure component liquid volume model for
all components (default)
1 Use steam tables for water
2 0 Use mole basis composition (default)
1 Use mass basis composition
VAQCLK 1 0 Use Clarke model
1 Use liquid volume quadratic mixing rule

5 Property Model Option Codes 279


Index

Brokaw/DIPPR viscosity model


A 213
Brokaw-Wilke mixing rule
Activity coefficient models 83 viscosity model 216
list of property models 83 Wilke-Lee (binary) diffusion
Andrade/DIPPR viscosity model model 242
207 Wilke-Lee (mixture) diffusion
Antoine/Wagner vapor pressure model 243
model 147 Chien-Null activity coefficient
API 1997 Liquid Viscosity 211 model 86
API model 160, 211, 249 Chung-Lee-Starling model 218,
liquid viscosity 211 220, 230
liquid volume 160 low pressure vapor viscosity 218
surface tension 249 thermal conductivity 230
API Sour model 152 viscosity 220
Applications 88 Clarke electrolyte liquid volume
metallurgical 88 model 161
Aqueous infinite dilution heat Clausius-Clapeyron equation for
capacity model 176 heat of vaporization 159
Aspen Liquid Mixture Viscosity 212 Coal property models 257
model 212 Constant activity coefficient model
Aspen polynomial equation 174 88
COSMO-SAC solvation model 88
B COSTALD liquid volume model 164
Criss-Cobble aqueous infinite
Barin equations thermodynamic
dilution ionic heat capacity
property model 190
model 177
Benedict-Webb-Rubin-Starling 17
property model 17
Braun K-10 model 152 D
Brelvi-O'Connell model 161 Dawson-Khoury-Kobayashi
Bromley-Pitzer activity coefficient diffusion model 244
model 83 binary 244
BWR-Lee-Starling property model mixture 244
16 DCOALIGT coal density model 266
Dean-Stiel pressure correction
C viscosity model 222
Debye-Huckel volume model 165
Cavett thermodynamic property
DGHARIGT char density model 266
model 190
Diffusivity models list 242
Chao-Seader fugacity model 153
DIPPR 7
Chapman-Enskog 213, 216, 242,
equations 7
243

280 Index
DIPPR model 156, 167, 181, 207, G
213, 233, 237, 249
General models for
heat of vaporization 156
nonconventional components
ideal gas heat capacity 181
255, 256, 260
liquid surface tension 249
coal model for enthalpy 260
liquid thermal conductivity 233
density polynomial model 256
liquid volume 167
enthalpy and density models list
surface tension 249
255
vapor thermal conductivity 237
heat capacity polynomial model
vapor viscosity 213
256
viscosity 207, 213
Grayson-Streed fugacity model 153
DIPPR/IK-CAPE model 177
Group contribution activity
liquid heat capacity 177
coefficient models 137, 139,
DNSTYGEN nonconventional
140
component density model 256
Dortmund-modified UNIFAC 139
Lyngby-modified UNIFAC 140
E UNIFAC 137
Electrolyte models 161, 193, 194,
223, 232, 245, 253 H
Clarke liquid volume 161
Hakim-Steinberg-Stiel/DIPPR
electrolyte NRTL enthalpy 193
surface tension 249
Gibbs energy 194
Hansen solubility parameter model
Jones-Dole viscosity 223
109
Nernst-Hartley diffusion 245
Hayden-O'Connell 20
Onsager-Samaras surface
property model 20
tension 253
HCOALGEN general coal model for
Riedel thermal conductivity 232
enthalpy 260
Electrolyte NRTL 91, 193, 194
Heat capacity models list 176
activity coefficient model 91
Heat of vaporization 156
enthalpy thermodynamic
model 156
property model 193
Helgeson thermodynamic property
Gibbs energy thermodynamic
model 201
property model 194
Henry's constant solubility
eNRTL-SAC activity coefficient
correlation model 187
model 104
HF equation of state 22
Enthalpies model based on
property model 22
different reference states 196
Huron-Vidal mixing rules 76
Enthalpy and density models for
coal and char 257
ENTHGEN nonconventional I
component heat capacity IAPS models for water 222, 231,
model 256 249
Equation-of-state 14 surface tension 249
property models 14 thermal conductivity 231
extrapolation 9 viscosity 222
Ideal gas law 26
F property model 26
Ideal gas/DIPPR heat capacity
Fugacity models list 147
model 181
Ideal liquid activity coefficient
model 110
IGT density model for 266

Index 281
char 266 property model 91
coal 266 NRTL-SAC 116
Using 121
J
O
Jones-Dole electrolyte correction
viscosity model 223 Onsager-Samaras electrolyte
surface tension model 253
K option codes
activity coefficient models 269
Kent-Eisenberg fugacity model 154 enthalpy models 276
equation of state models 271
L gibbs energy models 278
soave-redlich-kwong models 274
Lee-Kesler Plöcker property model
transport property models 268
28
Lee-Kesler property model 26
Letsou-Stiel viscosity model 225 P
Li mixing rule thermal conductivity Peng-Robinson 44, 46, 48, 66
model 232 alpha functions 66
Liquid Constant Molar Volume MHV2 property model 48
Model 166 property model 46
Liquid enthalpy 196 Wong-Sandler property model 48
thermodynamic property model Physical properties 11, 14
196 models 11, 14
Lucas vapor viscosity model 225 Pitzer activity coefficient model 122
Polynomial activity coefficient
M model 133
PPDS Heat of Vaporization
Mathias alpha function 70
Equation 157
Mathias-Copeman alpha function
PPDS Liquid Heat Capacity 179
66, 70
Predictive Soave-Redlich-Kwong-
Maxwell-Bonnell vapor pressure
Gmehling mixing rules 79
model 155
Predictive SRK property model
MHV2 mixing rules 78
(PSRK) 48
Modified MacLeod-Sugden surface
Property models 5, 11, 14
tension model 254
equation-of-state list 14
Modified Rackett model for molar
list of 5
volume 173
thermodynamic list 11
Molar volume and density models
PSRK 48
list 159
property model 48

N
R
Nernst-Hartley electrolyte diffusion
Rackett mixture liquid volume
model 245
model 171
Nonconventional solid property
Rackett/DIPPR pure component
models 255
liquid volume model 167
density 255
Redlich-Kister activity coefficient
enthalpy 255
model 135
list of 255
Redlich-Kwong 49, 70
Nothnagel 30
alpha function 70
property model 30
property model 49
NRTL 91

282 Index
Redlich-Kwong-Aspen property mixtures 248
model 49 models list 248
Redlich-Kwong-Soave 52, 54, 56, Modified MacLeod-Sugden 254
70
alpha function equations 70 T
alpha function list 70
Boston-Mathias property model Thermal conductivity 229, 236
52 models list 229
MHV2 property model 54 solids 236
Soave-Redlich-Kwong property thermo switch 7
model 56 Thermodynamic property 11, 190
Wong-Sandler property model 54 list of additional models 190
Redlich-Kwong-Soave property models list 11
model 50 Three-suffix Margules activity
Riedel electrolyte correction coefficient model 136
thermal conductivity model THRSWT 7
232 Transport property 204
models list 204
transport switch 7
S
TRAPP 227, 240
Sato-Riedel/DIPPR thermal thermal conductivity model 240
conductivity model 233 viscosity model 227
Scatchard-Hildebrand activity TRNSWT 7
coefficient model 135 Twu Liquid Viscosity 227
Schwartzentruber-Renon property
model 54 U
Soave-Redlich-Kwong property
model 56 UNIFAC 137, 139, 140
Solid Antoine vapor pressure activity coefficient model 137
models 155 Dortmund modified activity
Solid Thermal Conductivity coefficient model 139
Polynomial 236 Lyngby modified activity
Solids polynomial heat capacity coefficient model 140
model 185 UNIQUAC 141
Solubility correlation models 187 activity coefficient model 141
list 187 Units for Temperature-Dependent
SRK-Kabadi-Danner property Properties 6
model 58
SRK-ML property model 60 V
Standard Peng-Robinson property
Van Laar activity coefficient model
model 46
143
Standard Redlich-Kwong-Soave
Vapor pressure model list 147
property model 50
Viscosity 206
Steam tables 15, 29
models 206
NBS/NRC 29
property models 15
STEAMNBS property method 29 W
Stiel-Thodos pressure correction Wagner Interaction Parameter
thermal conductivity model activity coefficient model 144
239 Wagner vapor pressure model 147
Stiel-Thodos/DIPPR thermal Wassiljewa-Mason-Saxena mixing
conductivity model 237 rule for thermal conductivity
Surface tension 248, 254 241

Index 283
Water solubility model 188
Watson equation for heat of
vaporization 157
Wilke-Chang diffusion model 246,
247
binary 246
mixture 247
WILS-GLR property method 196
WILS-LR property method 196
Wilson (liquid molar volume)
activity coefficient model 146
Wilson activity coefficient model
145
Wong-Sandler mixing rules 81

284 Index